bluuebunny/crossref_metadata_2025_split huggingface dataset:
Cross-Sectional Preparation of Challenging Devices and Their Scale-Bridging Micro- and Nanoanalytical Characterization
Authors: Butz Benjamin , Hepp Marco , Derr Katharina 
Published: July 2022

Complex devices like batteries, fuel cells or organic sensors and solar cells are commonly assembled from multiple functional components with different materials properties. To gain a fundamental understanding of the microstructure-property relations of such complex macroscopic structures, their degradation and failure mechanisms by complementary scale-bridging microscopic and spectroscopic techniques, it is desirable to prepare cross sections of entire devices or parts. Most challenging is the generation of electron transparent cross-sectional samples for investigation by (cryo) transmission electron microscopy (TEM); preparing TEM samples of devices consisting of different material classes may be utmost difficult. Therefore, TEM sample preparation is often preceded by the disassembly of a device down to individual components rendering an investigation of relations between the individual components impossible.
(Cryo-)ultramicrotomy as well as plasma-FIB as advanced cross-sectioning techniques for challenging samples may solve those issues. Both are capable to generate ultra-thin, electron transparent cross sections of hundreds of micrometers in size being larger than the typical thickness of modern devices.
In this contribution, we demonstrate the capabilities of modern (cryo-)ultramicrotomy in conjunction with advanced TEM to characterize such sensitive or reactive and thus challenging devices down to the atomic scale. Examples include battery parts, PEM fuel cells and novel flexible all-organic electronics. The achieved thickness of those cross sections is commonly of the order of a few 10 nm, which even allows for atomic-resolution imaging and advanced spectroscopy for microstructure and defect analyses as well as compositional and chemical-bond investigation, respectively.

Hepp et al., Trained Laser-Patterned Carbon as High-Performance Mechanical Sensors, NPJ Flex. Electron. 6 (2022), 3, DOI: 10.1038/s41528-022-00136-0

Beaupain et al., Reaction of Li1.3Al0.3Ti1.7(PO4)3 and LiNi0.6Co0.2Mn0.2O2 in Co-sintered Composite Cathodes for Solid-State Batteries, ACS Appl. Mater. Inter. 13 (2021) 47488-47498, DOI: 10.1021/acsami.1c11750

Li et al., Atomic structure of sensitive battery materials and interfaces revealed by cryo-electron microscopy, Science 358 (2017), 506–510, DOI: 10.1126/science.aam6014

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(Digital Presentation) Electrochemical Synthesis of Highly Crystalline γ-NiOOH and Its Bifunctional Electrocatalytic Activity Towards Oxygen Evolution and Reduction Reactions in Alkaline Solutions
Authors: Rzeznicka Izabela Irena , Putra Ridwan Pratama , Horino Hideyuki 
Published: July 2022

Nickel (oxy)hydroxides are widely used as cathode materials in alkaline rechargeable batteries, including NiOOH-Cd, NiOOH-Zn and Ni-metal hydride batteries. NiOOH is a 2D-layered compound, known to exist in three different polymorphs α, β and γ. Compared with β-NiOOH, γ-NiOOH has a higher theoretical specific capacity and a lower self-discharge rate. However, when using a battery-grade Ni(OH)2, the β-NiOOH is mainly formed, which may transform to γ-NiOOH in the long run. Batteries based on β-NiOOH have poor life cycling and suffer from volume expansion. Therefore, γ-NiOOH is a desirable electrode material which can also be used in the next-generation high-capacity metal-air batteries due to its excellent electrocatalytic activity towards oxygen evolution reaction (OER).
In this presentation, we will report a new synthesis method of γ-NiOOH, in which only γ-phase is formed. The method is based on in-situ electrochemical transformation of a two-dimensional nickel chelate polymer in a carbon matrix in an alkaline electrolyte. γ-NiOOH prepared in this way is highly crystalline and has an excellent catalytic activity towards OER with overpotential of 390 mV at 12 mA/cm2. In addition, it can also catalyze oxygen reduction reaction (ORR), with an onset potential of 0.81 V vs. RHE in 1 M KOH.
Acknowledgements
The authors would like to thank Japan Society for Promotion of Science under the JSPS KAKENHI Grant Number JP 20K05689 for financial supports.
Nano-FTIR Correlation Nanoscopy for Organic and Inorganic Material Analysis
Authors: Gokus Tobias 
Published: July 2022

Significance: Correlation scanning probe techniques to complement nanoscale IR measurements for next generation sample characterization
Scattering-type Scanning Near-field Optical Microscopy (s-SNOM) is a scanning probe approach to optical microscopy and spectroscopy, bypassing the ubiquitous diffraction limit of light to achieve a spatial resolution below 20 nanometers. s-SNOM employs the strong confinement of light at the apex of a sharp metallic atomic force microscopy (AFM) tip to create a nanoscale optical hot-spot. Analyzing the scattered light from the tip enables the extraction of the optical properties of the sample directly below the tip and yields nanoscale resolved images simultaneous to topography [1]. In addition, the technology has been advanced to enable Fourier-Transform Infrared Spectroscopy on the nanoscale (nano-FTIR) [2] using broadband radiation from the visible spectral range to THz frequencies.
Recently, the combined analysis of complex nanoscale material systems by correlating near-field optical data with information obtained by other scanning probe microscopy (SPM)-based measurement methodologies has gained significant interest. For example, the material-characteristic nano-FTIR spectra of a phase-separated polystyrene/low-density polyethylene (PS/LDPE) polymer blend verifies sharp material interfaces by measuring a line profile across a ca. 1 μm sized LDPE island. Near-field reflection/absorption imaging at 1500cm-1 of the ca. 50nm thin film allows to selectively highlight the distribution of PS in the blend and simultaneously map the mechanical properties like adhesion of the different materials [3,4].
Further, we present results that correlate the near-field optical response of semiconducting samples like graphene (2D) or functional SRAM devices (3D) in different frequency ranges (mid-IR & THz) to Kelvin Probe Force Microscopy (KPFM) measurements. Thus, s-SNOM systems represent an ideal platform to gain novel insights into complex material systems by different near-field and AFM-based method.
[1] F. Keilmann, R. Hillenbrand, Phil. Trans. R. Soc. Lond. A 362, 787 (2004).
[2] F. Huth, et al., Nano Lett. 12, 3973 (2012).
[3] B. Pollard, et al., Beilstein J. of Nanotechn. 7, 605 (2016).
[4] I. Amenabar, et al., Nature Commun. 8, 14402 (2017).
Green Approach for Fabrication of Holey Graphene Based Electrode for Supercapacitor Application
Authors: Patole Shashikant 
Published: July 2022

Holey graphene, also known as perforated graphene is formed generating in-plane holes in basal planes of graphene based materials. By combining the advantages of holes and graphene, holey graphene based materials have attained significant research interest in energy storage systems due to the high surface and high electrical conductivity. In the present work, the holey graphene nanosheets are synthesized using ‘metal catalyst activation strategy’ using a green chemistry approach. The synthesized holey graphene nanosheets are studied in detail using various comprehensive characterization and electrochemical analysis techniques. The green chemistry based fabricated holey graphene nanosheets are directly used as an electrode material in the supercapacitor application. In the supercapacitive study, the fabricated electrode exhibits an efficient performance (high capacitance, rate capacity and stability) than its pristine form (graphene) due to the formation of highly pores morphology which provides stupendous electroactive sites and resistance free pathways for ionic interaction and transport. The presented results provide a new platform for employing green approach for fabricating holey graphene based materials as an electrode in energy storage systems.

Keywords:
Holey Graphene, Pores, Nanosheets, Green Chemistry, Supercapacitors

References:

[1] Green chemistry based fabrication of holey graphene electrodes for high-performance supercapacitors, Materials Letters, 271, 127793 (2020).
[2] Holey graphene: An emerging versatile material, J. Materials Chemistry A, 8, 918 (2020).
(Invited) High Surface Area N-Doped Carbon Fibers with Accessible Reaction Sites for All Solid State Lithium Sulfur Batteries
Authors: Zhu Hongli , Sun Xiao 
Published: July 2022

All solid-state lithium-sulfur batteries (ASSLSBs) are believed to deliver extremely higher energy density and remarkable safety than conventional Lithium-Sulfur batteries using liquid electrolytes. However, the low utilization of active material (sulfur) caused by sluggish reaction kinetics greatly hindered the development of ASSLSBs. It is significant to fabricate an advanced electrode where sulfur has efficient electron/ion accessibility. Porous carbon host, which has been widely used in liquid cells, is proposed to address the challenges. However, the conventional porous carbon host used in liquid cells can not be directly used in ASSLSBs, because the nonmobile solid electrolytes can not reach the sulfur confined in the pores buried deeply inside the carbon. An ideal porous carbon host should own a large specific surface area to provide sufficient sites for sulfur, but it is very critical that the pores should only locate at the out surface of the carbon. Till now, though many works reported the application of porous carbon in ASSLSBs, but none of them discussed the structure requirement of porous carbon. Here, for the first time, we discussed the ideal structure of the porous carbon and developed a polyacrylonitrile-derived porous carbon fibers (named PPCF) with a unique core-shell structure where a layer of micropores cover on dense core contributing to a high specific surface area.
Porous carbon fibers were successfully prepared through electrospinning and following carbonization and activation processes. This PPCF owns a unique core-shell structure where a layer of micropores is covered on the dense cores. A high specific surface area of 1519 m2 g-1 was achieved, and the micropores could effectively confine the sulfur avoiding the formation of bulky sulfur. More importantly, the pores mainly distributed on the outer surface which rendered remarkable ion access to sulfur, contributing to high sulfur utilization. The fibrous morphology enabled efficient electron conduction paths through effective percolation. Compared with the vapor grown carbon fibers (VGCF), a common carbon fiber with no surface pores, the cathode using PPCF exhibited improved reaction kinetics with an overpotential reduction by 149 mV. The reduced overpotential explains the faster kinetic and higher utilization of sulfur in S-PPCF-SE. In the dQ/dV measurement, S-PPCF-SE showed strong anodic/cathodic peaks with high intensity of 3156/4367 mAh g-1 V-1 which are significantly higher than 1010/1268 mAh g-1 V-1 in S-VGCF-SE, demonstrating a greatly improved reaction kinetics. The ASSLSBs using PPCF exhibited three times enhanced initial capacity of 1166 mAh g-1 at C/20. After 50 cycles, the capacity gradually decreased to 710 mAh g-1 and was maintained stable after 220 cycles at C/10. A remarkable capacity of 889 mAh g-1 at C/2 was achieved. In comparison, the ASSLSBs using VGCF as carbon additive delivered a low rate capacity of 100 mAh g-1 at C/2.
Effects of Local Graphitization on the Charging Mechanisms of Capacitive Microporous Carbon Supercapacitor Electrodes Application
Authors: Yin Huan , Shao Hui , Taberna Pierre Louis , Yin Huan 
Published: July 2022

Electrochemical double layer capacitors (EDLCs) store the charge by reversible adsorption of ions at the electrode/electrolyte interface. The optimization of EDLC performance needs to push further our basic understanding of the ion fluxes that occur during the charging/discharging process. Microporous carbon has been widely used as supercapacitor electrode material thanks to their tunable porosity and high specific surface area. However, most of the porous carbon materials have complex carbon structures, so that the mechanism is still poorly understood.
Using electrochemical quartz crystal microbalance technique (EQCM) technique, we studied the charge storage mechanisms of two nanoporous carbide-derived carbon (TiC-CDC) electrodes, namely CDC-800 synthesized at 800℃ and CDC-1100 synthesized at 1100℃. These two carbons have a similar porosity but the CDC-1100 sample shows more graphitic carbon microstructure. We found that a counter-ion adsorption process mainly controls the charging mechanism of CDC-800 (“V” shape m vs Q plot), while an expanded ion-exchange and counter-ion adsorption process is obtained for CDC-1100 (“U” shape). We show here that the local carbon structure affects the charging mechanism of electrical double layer capacitance, and a strong interaction between the anions and graphitic carbons explains these different behaviors. Our results provide more insights into the fundamental understanding of the carbon/electrolyte interface and the charge of the electrical double layer capacitance.
Figure 1. Electrode mass change versus charge during the polarization of CDC-800 (a) and CDC-1100 (b) coated Au electrodes in 2M EMI-TFSI/ACN electrolyte at the scan rate of 10 mV·s−1.

Figure 1
(Nanocarbons Division SES Young Investigator Award) Synthetic Biology Approaches for Overcoming Bottlenecks in Optical Nanocarbon Technologies
Authors: Boghossian Ardemis Anoush 
Published: July 2022

Bioengineering is the synthetic biologist’s approach to engineering new materials. It has allowed researchers to overcome billions of years of evolution to create unnatural biomolecules that have been programmed to interface with synthetic materials or optimized to bind analytes through interactions unfounded in nature. Biomolecules offer unparalleled molecular recognition that can be tuned by engineers to create highly specific sensors. Unfortunately, biology has its limits; many biological optical sensors rely on fluorophores that photobleach, which limit sensor lifetime, at visible emission wavelengths that overlap with tissue absorption. Unlike these fluorophores, semiconducting single-walled carbon nanotubes (SWCNTs) benefit from fluorescent emissions that are indefinitely photostable, demonstrating sensitivities that can detect analytes down to the single molecule. Their near-infrared fluorescence wavelengths are also transparent to tissue absorption, allowing for continuous in vivo sensing. Unfortunately, these nanomaterials lack the molecular recognition biology has to offer.
In a sense, the advantages and disadvantages posed by the fields of bio- and nano-materials engineering are highly complementary. This seminar focuses on the development of a new generation of NanoBiOptic devices – devices that exploit the synergy of nano-bio hybrids – for sensing applications. We apply bioengineering techniques, such as directed evolution and artificial nucleic acid design, to circumvent current approaches used to engineer SWCNT-based sensors. In demonstrating these techniques, we realize several previously intractable platforms for bioanalyte detection and for optically monitoring various biomolecular interactions. Thus, by reprogramming biological materials to behave in an otherwise non-natural manner, synthetic biology has the potential to complement the physical sciences in the engineering of new synthetic optical platforms.
(Invited) Engineering Antibodies Fragments for Continuous Protein Biosensing
Authors: Corrie Simon , Fercher Christian , Islam Jiaul , Jones Martina , Mahler Stephen 
Published: July 2022

Developing new approaches to monitor critical analytes in complex biological environments is key to the development of new diagnostic tools for application in a range of fields including the biomedical, environmental and food sciences. While reversible ion and metabolite sensing can be achieved through a variety of approaches including ionophore-based techniques, there is a lack of approaches to achieve real-time protein monitoring. Immunoassays (e.g. ELISA) are robust approaches to achieve endpoint measurements, however the multi-step nature of the technique is not amenable to reversible biosensing. One approach to simplify immunoassay chemistry is to reduce the number of assay steps required, which could lead to simpler manual assays, less reliance on laboratory infrastructure, or simpler POC designs.
We have developed a biosensor approach based on direct detection of antigen-antibody binding in a single step. Using a site-specific approach to incorporate fluorescent dyes into antibody fragments, we screened a range of positional mutants and identified several that showed antigen-dependent spectral changes. These changes were observed to be dose-dependent in both buffer and diluted plasma samples. We then applied a site-directed mutagenesis approach to generate antibody fragments capable of reversible protein interactions and reversible sensing. These fragments can be used in homogenous assays or immobilised to surfaces, and in this presentation we will present our most recent results on epidermal growth factor receptor (EGFR) and cardiac troponin I (cTnI) monitoring.
(Invited) Carbon Nanotubes for Plant Genetic Engineering
Authors: Demirer Gozde S , Zhang Huan , González Grandío Eduardo , Landry Markita P 
Published: July 2022

Plants will benefit from genetic engineering to feed our growing global population in the midst of climate change, to provide our most clinically-relevant drugs, and for our environmental remediation efforts. New generation genome engineering technologies, such as CRISPR/Cas, hold the potential to alter plant genes in a precise and targeted manner. The first step of any plant genetic engineering application is to deliver important biomolecular cargoes into the desired subcellular locations of plant cells. However, the limitations of traditional plant gene delivery methods, i.e. Agrobacterium and gene gun, prevent plant genetic engineering from reaching its full potential.
Given the lack of efficient biomolecule delivery vehicles to plants and potential impact of plant biotechnology on food security and sustainability, we developed nanoparticle-based platforms to efficiently deliver small interfering RNA1,2 and plasmid DNA3,4 cargoes into plant cells in a species-independent manner, which eliminates the use of gene gun and addresses the main delivery bottlenecks of plant genetic engineering. We show that pristine single walled carbon nanotubes (SWCNTs) can adsorb small interfering RNA molecules through pi-pi stacking for plant delivery, whereas a covalently modified and positively charged SWCNT platform is more efficient for large double-stranded DNA delivery to mature plant leaf cells.
This talk will first briefly summarize the development, characterization and biological verification of each nanoparticle platform for plant delivery applications. Next, I will present our recent results of CRISPR/Cas gene editing in plant leaves using the SWCNT DNA delivery platform5. The talk will be concluded by discussing the several assays performed to demonstrate the effect of nanoparticles on plant health, including an RNA-sequencing analysis of nanoparticle-treated plant leaves6. We believe the SWCNT delivery technologies that are discussed in this talk will have an immense impact on food security and sustainability by enabling the generation of improved plants that can rapidly reach the market in a cost-effective manner.

Demirer G.S.*, Zhang H.* et al., DNA Nanostructures Coordinate Gene Silencing in Mature Plants. PNAS (2019).

Demirer G.S. et al., Carbon Nanocarriers Deliver siRNA to Intact Plant Cells for Efficient Gene Knockdown. Science Advances (2020).

Demirer G.S. et al., High Aspect Ratio Nanomaterials Enable Delivery of Functional Genetic Material Without Transgenic DNA Integration in Mature Plants. Nature Nanotechnology (2019).

Demirer G.S. et al., Carbon nanotube–mediated DNA delivery without transgene integration in intact plants. Nature Protocols (2019).

Demirer G.S. et al., Nanotechnology to advance CRISPR–Cas genetic engineering of plants. Nature Nanotechnology (2021).

González-Grandío E., Demirer, G.S. et al. Carbon nanotube biocompatibility in plants is determined by their surface chemistry. bioRxiv (2021).
An Algorithmic Approach for Developing Single-Walled Carbon Nanotube Optical Sensors Against Adulterants in Aquaculture
Authors: Gong Xun , Renegar Nicholas , Cho Soo-Yeon , Levi Retsef , Strano Michael 
Published: July 2022

The nanoparticle corona phase (CP) offers a unique materials design space for constructs capable of molecular recognition (MR) for sensing applications. Single-walled carbon nanotube (SWCNT) CPs have the additional ability to transduce MR through its band gap photoluminescence (PL). DNA oligonucleotides are well-known to disperse SWCNTs through forming CPs and can be manufactured with molecular precision. Nevertheless, no generalized scheme exists for the de novo prediction of SWCNT MR based on these CPs due to their sequence-dependent three-dimensional complexity.
In aquaculture, there exist a pressing need for rapid tests for the detection of commonly harmful adulterants such as metal ions and small molecule antibiotics. Through a screening process, we found that DNA-SWCNTs offer a rich design space for MR capable of differentiating divalent metal ions. We also created best practices for the study of colloidal SWCNT analyte responses involve mitigating the effects of ionic strength, dilution kinetics, laser power and analyte response kinetics.
Next, we generated the largest DNA-SWCNT PL response library of 1408 elements against 4 adulterant targets. We leveraged machine learning (ML) techniques and used both local features (LFs) and high-level features (HLFs) of the DNA sequences were utilized as model inputs. Out-of-sample analysis of our ML model showed significant correlations between model predictions and actual sensor responses for 6 out of the 8 tested experimental conditions. Furthermore, models utilizing both LFs and HLFs show improvement over that with HLFs alone, demonstrating that DNA-SWCNT CP engineering is more complex than simply specifying general DNA molecular properties. Taken as a whole, we detail the feasibility and utility of a ML-guided approach for nanoparticle CP engineering with relatively few experiments within a high-dimensional design space.
(Invited) Hyperspectral Detection of the Fluorescence Shift between Enantiomers of Empty and Water-Filled Single-Wall Carbon Nanotubes
Authors: Wenseleers Wim , Erkens Maksiem , Lopez Carrillo Miguel Angel , Botka Bea , Cambre Sofie , Duque Juan 
Published: July 2022

The unusually chiral-structure-dependent properties of single-wall carbon nanotubes (SWCNTs) are also strongly influenced by their internal and external environment, which can therefore be investigated through optical spectroscopy.[1,2] In order to study this influence in detail, we developed a hyperspectral IR fluorescence imaging setup based on a microscope with a liquid crystal tunable filter. By resolving the spectra of individual SWCNTs, and even along the length of SWCNTs, the effect of inhomogeneous broadening is largely eliminated, and spectral details can be resolved which are inaccessible in bulk spectroscopy. An automated image processing scheme is used to obtain statistics on large numbers of individual SWCNTs. In particular, we show that not only the spectral shift in emission between empty and water-filled[1] chirality sorted SWCNTs can be resolved, but even separate emission peaks are observed for the left- and right-handed enantiomers, which interact slightly differently with the chiral surfactant with which they are coated. The approach is particularly promising for the quantification of enantio-selective separation results.
[1] W. Wenseleers et al., Adv. Mater. 19, 2274 (2007); S. Cambré and W. Wenseleers, Angew. Chem. 50, 2764 (2011); S. Cambré et al., ACS Nano
6, 2649 (2012).
[2] J. Campo et al., ACS Nano 2021, 15, 2301−2317.