bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Electrochemical Preparation of Micro and Nano Structures and Systems in Silicon for (Bio)Sensing and Nano(Medicine) Applications
Authors: Barillaro Giuseppe 
Published: February 2020

When dealing with biosensing and nanomedicine applications the length scale of targets may vary over more than 5 orders of magnitude moving from the molecular level (0.1-1 nm) up to the cell level (1-10 μm). A number of micro and nanostructuring technologies have been developed over the years to enable the preparation of both structures and systems with length scales suitable to match specific biological targets.
In this talk, electrochemical preparation of nano and micro structures and systems in silicon with length scales spanning over 5 order of magnitudes, able to target different applications both in (nano)medicine (e.g. sinusoid-like liver on a chip, nanopillars for cell transfection, 3D microincubators for tumor cell screening) and (bio)sensing (e.g. microneedles for transdermal biosensing, optical biosensors for point-of-care clinical diagnostics, chemitransitor sensors for environmental monitoring), is presented and discussed.
1. S.Mariani, V. Robbiano, L. M. Strambini, A. Debrassi, G. Egri, L. Dähne, G. Barillaro, Layer-by-layer biofunctionalization of nanostructured porous silicon for high-sensitivity and high-selectivity label-free affinity biosensing, Nature Communications, 9, 5256, 1-13 (2018)
2. B. Delalat, C. Cozzi, S. R. Ghaemi, G. Polito, F. E. Kriel, T. D. Michl, F. J. Harding, C. Priest, G. Barillaro, N. H. Voelcker, Microengineered Bioartificial Liver Chip for Drug Toxicity Screening, Advanced Functional Materials 1801825 (2018).
3. Robbiano, G. M. Paterno, A. A. La Mattina, S. G. Motti, G. Lanzani, F. Scotognella, G. Barillaro, Room-Temperature Low-Threshold Lasing From Monolithically Integrated Nanostructured Porous Silicon Hybrid Microcavities, ACS Nano12, 4536−4544 (2018).

4. J. Harding, S. Surdo, B. Delalat, C. Cozzi, R. Elnathan, S. Gronthos, N. H. Voelcker, G. Barillaro, Ordered Silicon Pillar Arrays Prepared by Electrochemical Micromachining: Substrates for High-Efficiency Cell Transfection, ACS Applied Materials and Interfaces, 8 (43), 29197-29202 (2016).

5. Mariani, L. M. Strambini, G. Barillaro, Femtomole Detection Of Proteins Using A Label-Free Nanostructured Porous Silicon Interferometer For Perspective Ultra-Sensitive Biosensing, ACS Analytical Chemistry, 88 (17), 8502-8509 (2016).
6. Mariani, L. Pino, L. M. Strambini, L. Tedeschi, G. Barillaro, 10000-Fold Improvement in Protein Detection Using Nanostructured Porous Silicon Interferometric Aptasensors, ACS Sensors, 1, 1471-1479(2016).
7. M. Sainato, L.M. Strambini, S. Rella, E. Mazzotta, G. Barillaro, Sub-Parts Per Million NO2 Chemi-Transistor Sensors Based on Composite Porous Silicon/Gold Nanostructures Prepared by Metal-Assisted Etching, ACS Applied Materials and Interfaces 7, 7136 (2015).
8. M. Strambini, A. Longo, S. Scarano, T. Prescimone, I. Palchetti, M. Minunni, D. Giannessi, G. Barillaro, Self-Powered Microneedle-Based Biosensors for Pain-Free High-Accuracy Measurement of Glycaemia in Interstitial Fluid, Biosensors and Bioelectronics,66, 162 (2015).
Layer-By-Layer Biofunctionalization As a Novel Route for High-Sensitivity and High-Specificity Label-Free Affinity Biosensing with Nanostructured Materials
Authors: Mariani Stefano , Robbiano Valentina , Strambini Lucanos , Debrassi Aline , Egri Gabriela , Daehne Lars , Barillaro Giuseppe 
Published: February 2020

Nanostructured materials hold the promise to revolutionize the label-free biosensing of analytes at concentrations down to those required for clinical applications, beyond what microstructured materials did so far, by leveraging the deeper interaction between materials and analytes with comparable size. On the other hand, when the characteristic dimension of the materials gets down to the nanoscale, the biofunctionalization chemistry commonly used to promote the binding of bioreceptors and enable, in turn, the specific detection of target analytes becomes less effective.
Here, we propose an effective and robust route for the surface biofunctionalization of nanostructured materials based on the layer-by-layer electrostatic nano-assembling of oppositely-charged polyelectrolytes, which were engineered with bioreceptors covalently linked to the polymer chain. LbL biofunctionalization allows stability, density, and distribution of bioreceptors available on the transducer surface to be carefully controlled, thus solving most of the drawbacks of the common biofunctionalization chemistry on nanostructured materials.
The proof-of-concept demonstration of advantages of LbL biofunctionalization is given on nanostuctured porous silicon (PSi) interferometers, which are biofunctionalized for the affinity detection of streptavidin in raw saliva via LbL nano-assembling of a positively-charged poly(allylamine hydrochloride) (PAH) with a negatively-charged biotinylated poly(methacrylic acid) (b-PMAA). LbL-biofunctionalizion of PSi interferometers results to be very effective and highly robust, enabling high-sensitivity and high-specificity detection of streptavidin with a detection limit of 600 fM. This represents a 100000-fold improvement with respect to control PSi interferometers biofunctionalized using common silane-based chemistry and a 300-fold improvement with respect to best PSi label-free biosensors reported in the current literature, pushing PSi optical biosensors to performance comparable to those of best label-free plasmonic and photonic platforms.
[1] Layer-by-layer biofunctionalization of nanostructured porous silicon for high-sensitivity and high-selectivity label-free affinity biosensing, S Mariani, V Robbiano, LM Strambini, A Debrassi, G Egri, L Dähne, G. Barillaro, Nature Communications 9 (1), 5256 (2018)
Understanding How Structure Influences Electrochemical Behavior When ZnO Is Used to Suppress Aluminum Corrosion in Alkaline Electrolytes
Authors: Faegh Ehsan , Shrestha Sujan , Zhao Xinyi , Mustain William E. 
Published: February 2020

The severe corrosion rate of aluminum (Al), coupled with hydrogen evolution (H2 gassing), is the major roadblock preventing the widespread deployment of Al as the anode material in primary and secondary alkaline batteries. One of the most successful approaches to reduce this corrosion has been the addition of ZnO to the alkaline KOH electrolyte, which results in the spontaneous electroless deposition of a protective metallic Zn film on the Al surface. However, the fundamental structural and electrochemical characterization of Zn on Al as well as the influence of ZnO/KOH composition need to be investigated.
This study aims to develop a novel fundamental understanding of the protection mechanism against Al corrosion when zincate (from dissolved ZnO) is added to KOH electrolytes. The effects of both ZnO concentration and KOH concentration are probed. Morphological studies of the spontaneous Zn film were realized using SEM, XRD, N2 adsorption and measurements of real time H2 gas evolution. These were coupled with discharge experiments to create a new structure-function understanding for ZnO protection of Al. It should be noted that electrolytes enabling protective Zn films with good adherence and density were found, and capacities near the Al theoretical capacity were achieved.
(Invited) Diamond Electrodes for Electro-Chemical Synthesis
Authors: Mollart Tim , Zarrin Hossein 
Published: February 2020

Boron doped diamond (BDD) electrodes have remarkable electrochemical properties, they are enabling novel electrochemical processes, from advanced oxidation liquid waste treatment to new types of electrochemical sensors and emerging new environmental processes. As an allotrope of carbon the properties of diamond electrodes have been shown to be a function of their crystallinity, boron doping concentration and non diamond (graphitic) carbon content. Optimized solid free-standing (not a coating) electrodes with high crystallinity and heavily boron doped can have solvent windows > 4 V (versus SCE) combined with metal like conductivity.
Many industrial chemical processes can benefit from the ability of diamond electrodes to deliver high oxidation and reduction potentials while suppressing the electrolysis of water. In the anodic region due to their high physical, chemical and electrochemical stability the hydroxyl and sulfate radical can be formed enabling direct or indirect electrochemical oxidation of dissolved species in the electrolyte. At the anode species such as nitrates can be reduced to nitrogen and since water electrolysis is suppressed in some conditions these processes can be carried out at near 100% Faraday current efficiencies
Diamond electrodes are being used in electrochemical advanced oxidation processes (AOPs) for removal of recalcitrant organic pollutants in the industrial liquid wastes by mineralizing them to CO2 and H2. Hydroxyl radicals have a high oxidation potential (2.80V) when compared to ozone (2.08V) and hydrogen peroxide (1.27V) and since the formation takes place directly at the anode by electrochemical oxidation, these systems have been found to be highly effective and universally applicable.
In environmental processing and recycling electro oxidation is emerging as a way of making closed cycle chemical processes for e.g. materials recovery from wastes and regeneration of process effluents. Diamond electrodes can be used to simultaneously remove dissolved organics contaminants and restore the oxidation potential of a process effluent. Enables a reduction of the need for chemical dosing and the disposal of chemical wastes. In this talk we will explore some examples of these new electrochemical processes and discuss the potential for new processes that exploit the cathodic properties of diamond electrodes.
Investigation of Cell Microenvironment Effect on Cell Behaviors Using Electrochemical Scanning Probe Microscopy
Authors: Li Fei 
Published: February 2020

Cell microenvironment (chemical, mechanical, electric) directly effects cell functions and behaviors (biology, mechanics, electrophysiology). Study of cell microenvironment effect on cell functions and behaviors is important for understanding the pathological mechanism of diseases (heart disease, cancer). Different kinds of hydrogels, which is an ideal material to mimic 3D extracellular matrix (ECM) of cell, have been developed and used to construct 3D cell microenvironment in vitro. To understand the effect of cell microenvironment constructed by hydrogels on cell behaviors, the technique which can characterize both the property of hydrogels and the topography and multi-behaviors of cells at mm/nm scale in an in-situ, non-damage way is needed. Scanning electrochemical microscopy (SECM) and scanning ion conductance microscopy (SICM) are two kinds of electrochemical scanning probe microscopy with the capability of providing morphology and performing chemical analyses of cells in an in situ, reversible and non-destructive way.
In our work, we firstly constructed cell microenvironment based on three kinds of functional hydrogels (i.e., self-healing hydrogels, magnetic hydrogels and hydrogel microwell arrays). Then SECM was applied to in-situ track the self-healing process of hydrogel, the H2O2 consumption across magnetic hydrogel nanocomposites and the oxygen permeability across hydrogel microwell arrays. The effect of mechanical microenvironment on the redox state of cardiomyocytes and cardiac fibroblasts was also characterized by SECM. To further characterize the cell morphology at nm-scale, we also home built our SICM system and used it to characterize the cell morphology and cell volume on hydrogels with different stuffiness.

Figure 1
Ex Situ and Operando Characterization of Energy Storage Materials By Benchtop XAFS and XES
Authors: Jahrman Evan , Ditter Alex , Holden William , Pellerin Lisa , Seidler Gerald T. , Bradshaw Liam , Polzin Bryant J. , Fister Timothy T 
Published: February 2020

Advanced x-ray spectroscopies permit the interrogation of a material’s local electronic structure in an element-specific manner. In particular, these techniques reveal the speciation and ligand environment of an electroactive element and can provide direct insight into the state-of-charge and state-of-health of a battery. Despite their utility, the scientific impact of advanced x-ray spectroscopies is necessarily constrained by the availability of instrumentation. For x-ray absorption fine structure (XAFS) and x-ray emission spectroscopy (XES), studies are traditionally performed at synchrotron x-ray facilities. These facilities frequently serve to push the forefront of science and, as a result, necessarily operate under an access model which excludes projects which require routine analytical characterization, rapid feedback, or regular access.
Over the last four years, our group at the University of Washington has developed several families of laboratory-based instruments to expand the accessibility of advanced x-ray spectroscopies. For the study of transition metal chemistry, we have constructed two Rowland circle spectrometers based upon related designs. Both spectrometers provide energy resolutions comparable to that observed at a synchrotron endstation. Their designs are also highly efficient, allowing studies to be completed with commercial x-ray tube sources in time scales relevant for materials research programs. For many such studies, the instrumentation can generate satisfactory spectra in a matter of minutes, permitting operando studies of battery materials at charge rates in excess of 1C.
From the standpoint of instrumentation, a brief review of the present designs is presented with emphasis on recent advances in extended-XAFS capabilities. Differences between the spectrometer designs and the advantages of each will also be highlighted. Regarding materials inquiry, a survey of the above instrument’s application to energy storage research is provided. This will include XAFS analyses of two systems of nanoparticle compounds which were engineered to be catalysts or pseudocapacitors. These results will facilitate a review of the information attainable from the underlying technique. The rich electronic structure of vanadyl phosphate cathode materials, as well a suite of vanadium oxides, is probed via valence-to-core XES (VTC-XES). Finally, operando x-ray absorption near-edge structure (XANES) results obtained from a pouch cell containing a nickel-rich NMC cathode at a variety of charge rates are presented.
Operando SANS and Synchrotron Radiography Characterization of the Carbon Cathode from Lithium Sulfur Batteries
Authors: Jafta Charl J , Risse Sebastian , Prévost Sylvain , Trapp Marcus , Dai Sheng , Ballauff Matthias 
Published: February 2020

In recent years lithium sulfur (Li-S) battery research became an important route to go beyond traditional lithium ion batteries. Among various battery systems, Li-S batteries have comparatively high theoretical energy density and lower cost, making Li-S batteries very promising for next generation secondary batteries. However, the current energy density achieved, and significant capacity decay with cycling, do not fulfill the needs for industrialization. To overcome the drawbacks of Li-S batteries and improve their performance, better understanding of the reaction mechanism and how this relates to capacity decay is necessary. A great deal of ex-situ characterization research has been conducted that has shed light on the working mechanism. Considering the complexity of the solution and interfacial chemistry, with multiple intermediate lithium polysulfides and the inherent multi-electron reaction pathways, we developed advanced operando techniques to provide new information on the dynamic processes occurring at the electrode interface.
In this presentation operando small angle neutron scattering (SANS) results will be shown, specifically shedding light on the precipitation process of S8 and Li2S as a function of state of charge. We address the question of whether precipitation of S8 and Li2S in the charged and discharged states, respectively, occurs in the pore or on the surface of the carbon cathode. This is a question that enjoyed very little discussion, due to the challenges in directly measuring the precipitation. Operando radiographic evidence will also be shown regarding the distribution of precipitates in the electrode. These results will increase the understanding of the charge / discharge mechanism of Li-S batteries and will contribute to the advancement of this battery chemistry.
Recent Mechanistic Understanding of Oxygen Reduction Reaction over Pt-Supported 3D Carbon Nanofiber Catalysts
Authors: Liu Bin , Xu Jiayi , Elangovan Ayyappan , Li Jun 
Published: February 2020

For both proton exchange membrane and direct methanol fuel cells, oxygen reduction reaction (ORR) is a performance-determining step. While Pt has been established as a standard bearer in ORR catalyst development, practical long-term applications require continuing effort to pursue active, stable, as well as affordable materials as alternatives to precious metals.
In this talk, carbon-based vertically aligned carbon nanofibers (VACNFs), essentially a stack of conical graphitic structures, will be discussed as highly promising ORR catalysts. In an alkaline medium, at -0.4 V applied potential, the current density measured on VACNF cathode is twice more than that measured with commercial Pt catalyst (Pt/C). Molecular insights have been gained through the use of Density functional theory (DFT) calculations to: (1) reveal interactions of ORR intermediate species at the catalytically active sites; and (2) elucidate the origin of catalytic activities of VACNF under reaction conditions. Specifically, semi-periodic fishbone-like stacked graphene sheets, bare or terminated with H and OH, have been employed to understand the impact on ORR mechanism and corresponding reactivities. Bindings of O2, O, and OH at various configurations obtained from DFT are then used as descriptors to assess catalyst performance against simple Pt (111) and Pt (211) surfaces.
In addition, Pt nanocatalysts supported on VACNF (Pt/VACNF), which can push the ORR current density even higher, will be discussed as well. Again, with DFT, a model with Pt anchored at the VACNF edges was proposed to investigate the functionalities of Pt/VACNF for alkaline ORR reactions. In this talk, both associative and dissociative ORR pathways will be analyzed based on the established models. In particular, the overall computed ORR thermodynamics are shown to be favored toward Pt/VACNF than Pt (111), consistent with experimental results. Nevertheless, the unique interactions of ORR intermediates such as O*, OOH*, and OH* with catalytic active VACNF edge sites, revealed by DFT calculations, suggest intriguing but also complex electrochemistries.
(Nanocarbons Division Richard E. Smalley Research Award Address) Multifunctional Hybrid Carbon Interfaces
Authors: Prato Maurizio 
Published: February 2020

Carbon nanomaterials, including nanotubes and graphene, are particularly well suited for the design and construction of functional interfaces. This is mainly due to the extraordinary properties of these novel materials, which combine mechanical strength, thermal and electrical conductivity.
Our group has been involved in the organic functionalization of various types of nanocarbons, including carbon nanotubes, fullerenes and, more recently, graphene. The organic functionalization offers the great advantage of producing soluble and easy-to-handle materials. As a consequence, since biocompatibility is expected to improve upon functionalization, many modified carbon nanomaterials may be useful in the field of nanomedicine.
During this talk, we will show the latest and most exciting results obtained in our laboratories for applications of carbon nanomaterials in biology, medicine and energy.
Modeling the Charge and Discharge Behaviors of an AGM Lead-Acid Battery
Authors: Lee Jaewoo , Koo Boram , Shin Chee Burm 
Published: February 2020

An absorbent glass mat (AGM) lead-acid battery is a type of valve-regulated lead-acid (VRLA) battery. An AGM lead-acid battery differs from a flooded lead-acid battery in that the sulfuric acid is absorbed in a very fine fiberglass mat, making the battery spill-proof. The leading advantages of AGM type are a higher specific power, lower internal resistance, five times faster charge speed than the flooded version, and the ability to deep cycle. AGM lead-acid batteries are found in high-end vehicles equipped with more electronic devices and making inroads into the start-stop function of cars. A validated mathematical model for the accurate prediction of the charge and discharge behaviors of an AGM lead-acid battery in real-world driving conditions is necessary to ensure that the battery can provide enough power for the rising number of electrical components.
In this work, a method of modeling the charge and discharge behaviors of an AGM lead-acid battery under various operating conditions is presented. This work adopts a simple modeling approach by considering Ohm’s law and charge conservation on the electrodes based on the simplified polarization characteristics of the electrodes. By not computing the potential distribution of electrolyte phase and the transport phenomena of ionic species, the modeling method in this work cuts down considerable computation time in comparison with rigorous electrochemical models. The model is validated by comparing the modeling results with the experimental measurements.