bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electroorganic Synthesis of Tertiary Cyanoformamide from Trichloroacetonitrile Catalyzed By B12 Complex
Authors: Mohammad Moniruzzaman , Hisaeda Yoshio , Shimakoshi Hisashi 
Published: July 2021

Cyanoformamide is the key motifs of pharmaceuticals, agricultural chemicals, and component of the natural products, and it is vital building block in the synthesis of lactams,acrylonitriles, tetrazoles, unsymmetrical ketones, symmetric & asymmetric substituted ureas, and other heterocyclic compounds.[1] Herein the one-pot procedure for synthesis of tertiary cyanoformamide has been developed with electrochemical method by B12 complex[2] as catalyst under mild conditions, at room temperature under air. Over thirty examples of cyanoformamide were synthesized in moderate to good yields. This user-friendly strategy is compatible with a broad range of biologically active cyanoformamide and easily scalable with the cheap and simple experimental set-up.
References
[1] Y. Gao, Z. Zhang, Z. Li, T. Guo, Y. Zhu, Z. Yao, B. Liu, Y. Li, K. Gao, J. Org. Chem. 2020, 85, 1087.
[2] (a) Y. Anai, K. Shichijo, M. Fujitsuka, Y. Hisaeda, H. Shimakoshi, Chem. Commun., 2020, 56, 11945. (Inside front cover), (b) H. Shimakoshi, Z. Luo, T. Inaba, Y. Hisaeda, Dalton Trans, 2016, 45, 10173.

Figure 1
Electrochemical Investigations of Tau Protein Biochemistry
Authors: Martic Sanela 
Published: July 2021

Proteins play important biological functions and are commonly associated with a variety of diseases. One such protein is tau protein, which maintains brain cell function and is linked to neurodegeneration. The complex tau protein biochemistry is composed of the post-translational modifications, interactions with binding partners and aggregation, among other pathways. To investigate the complex biochemistry of tau protein, we utilized electrochemical methods (cyclic voltammetry and electrochemical impedance spectroscopy. We demonstrated detection of protein-protein interactions (1), protein-ligand interactions (2), enzymatic catalysis and enzyme inhibition (3). For this purpose, tau protein film on Au surface was fabricated and characterized. Tau-Au films were used to probe interactions with heparin, ferritin, transferrin, antibodies, and protein kinases. Our data indicate that tau-Au films are functional surfaces which allow for monitoring biomolecular interactions, and enzymatic transformations.
References
(1) a) Carlin, N., Martic-Milne (2018) J. Electrochem. Soc. 165: G3018-G3025. b) Jahshan, A., Esteves, J.O., Martic-Milne (2016) J. Inorg. Biochem. 162: 127-134.
(2) Trzeciakiewicz, H., Esteves, J. O.V., Carlin, N., Martic, S. (2015) Electrochim. Acta 162: 24-30.
(3) Esteves, J.O.V., Martic-Milne, S. (2016) Anal. Biochem. 496: 55-62.
Polarization Behaviors of Biofilms on Metallic Materials By E.coli and S.Epidermidis, and the Applicability of Results
Authors: Kanematsu Hideyuki , Ogaki Sho , Sugino Noe , Hirai Nobumitsu , Wada Noriyuki , Kogo Takeshi , Yamada Hirohisa , Tsunashima Katsuhiko , Barry Dana M. 
Published: July 2021

Biofilms are formed on materials by bacterial activities and bring about detrimental problems as well as beneficial ones in industrial fields and our daily lives. It is very important to establish effective countermeasures, to control biofilms properly and also to monitor the formation and growth. For any of those purposes, we have to know how the biofilms are constructed, what kind of components they have and also what is going on inside biofilms. Generally, we already know that biofilms are composed of dominated water, bacteria themselves and external polymeric substance (EPS) at the initial stages. From the academic viewpoints, the initial structures are illustrated very clearly and precisely and already well known. However, biofilms changes with time significantly. Inorganic and organic substances are introduced into biofilms from environments or substrates outside biofilms. They interact each other to form many new compounds or to decompose into new ones. And they break down due to many reasons. Since those interactions would be very complicated, lots of information about biofilms growth have been still missing. And the lack of information might bottleneck the development of countermeasure. Therefore, we need more effective investigations using various approaches. There is no doubt that electrochemical methods are very promising methods.
In this experiment, we chose two kinds of bacteria, E.coli and S.epidermidis. Each is representative gram-negative bacteria and gram-positive ones, respectively. Using those bacteria, biofilms formed on some metallic materials, such as copper and titanium. During the formation and growth of biofilms, the natural immersion potential (open circuit potentials) changed with time. However, the behaviors differed from substrate material to substrate material and also from bacteria to bacteria. And at some specific growth stages, the polarization curves were measured. The cyclic polarization curves depended also on the growth stage of biofilms.
The following results were obtained.
1. On the metallic materials forming biofilms easily such as copper, the natural immersion potentials shifted in the less noble direction with biofilm formation and growth significantly.
2. On the metallic materials with few biofilm formation/growth such as titanium, the natural immersion potentials did not change so much.
3. The polarization curves showed typical current peaks around 0.1-0.2V (versus Ag/AgCl in 3.3N KCl solution), when biofilms formed on metallic substrates.
4. In the case of few biofilm titanium specimens, polarization curves did not show any specific current peaks.
5. All of those electrochemical behaviors could be applied to monitor biofilms growth stages.
(Student Battery Slam Best Presentation Award Winner) Combining Experimentation and Computation for Accelerated Understanding of Electrode Morphology in Redox Flow Batteries
Authors: Tenny Kevin M. , Chiang Yet-Ming , Brushett Fikile R. 
Published: July 2021

Redox flow batteries (RFBs) hold promise as an electrochemical intermediary between intermittent renewable power generation and the grid.1 Within the RFB architecture, porous electrodes are an integral component, contributing to a myriad functions, such as providing surface sites for redox reactions, dispersing electrolyte throughout the void matrix, and shuttling electrons through its conductive network.2 Carbonaceous materials, such as cloths, papers, and felts, are commonly used in state-of-the-art RFB embodiments, despite their tailored morphologies in polymer electrolyte fuel cells. Consequently, these media engender suboptimal performance in RFBs, necessitating advancement of electrode structures specifically designed for flow battery operation.
While there have been previous systematic studies of RFB electrode structure/function relationships,3,4 most have been limited by manufacturing constraints, restricting the explorable design space. However, recent computational efforts have enabled broad sweeping property analyses,5 leveraging both data science and machine learning algorithms to identify key parameter values. These modeling and statistical pursuits, combined with advanced cell diagnostics, provide a platform for high-throughput material screening in the furtherance of electrode engineering.
In this presentation, we highlight some of the computational tools we have developed for simulated analyses of electrode functionalities in RFBs. We then present experimental tools for in situ and operando electrode benchmarking, which can also be simulated with the aforementioned computation toolkit. Finally, we conclude by demonstrating how this combined platform can be used across a wide variety of electrode domains, revealing performance comparisons and micron-scale designs to direct manufacturing avenues.
Acknowledgments
This work was funded by the Joint Center for Energy Storage Research, an Energy Innovation Hub of the U.S. Department of Energy, Office of Science, Basic Energy (De-AC02-06CH11357). K.M.T. recognizes additional support from the U.S. NSF Graduate Research Fellowship (1122374).
References

A. Z. Weber et al., J. Appl. Electrochem, 41, 1137 (2011).

K. J. Kim et al., J. Mater. Chem. A, 3, 16913–16933 (2015).

A. Forner-Cuenca, E. E. Penn, A. M. Oliveira, and F. R. Brushett, J. Electrochem. Soc., 166, A2230–A2241 (2019).

K. M. Tenny, A. Forner-Cuenca, Y.-M. Chiang, and F. R. Brushett, J. Electrochem. En. Conv. Stor, 17 (2020).

Z. Cheng et al., Applied Energy, 279, 115530 (2020).
Effect of Electrolyte Composition on the Performance of Coal Char-Derived Carbon Supercapacitors
Authors: Karimi Zahra , Moon Jaron V , Ginkel Chanel Van , U1302137 Douglas , Malzahn Joshua , Eddings Eric , Warren Roseanne 
Published: July 2021

Research regarding supercapacitors has vastly grown over the past decade. The advantages of supercapacitors include high power density, rapid charge/discharge capability, and a long cycle life. Current applications of supercapacitors are limited by the need to develop new, low-cost electrode materials for electric double layer capacitors and pseudocapacitors [1]. Coal char is the solid product of a low-temperature coal carbonization process, and is currently used primarily as an ultra-low-cost fuel for electric power generation. As such, coal char consists mainly of hard carbons and ash [2]. Upon ash removal, the hard carbons in coal char may serve as a promising, low-cost, supercapacitor electrode material. This research will present the use of inexpensive coal char as an electrode material for supercapacitors, with particular focus on the effects of various electrolyte compositions on the performance of coal-derived carbon supercapacitors.
Electrolyte composition plays a large role in the electrochemical properties of a supercapacitor, affecting: ion interactions with electrode surface functional groups; electric double layer capacitance; thermal stability; and allowable voltage range. In this work, bituminous grade coal char from a Utah mine is pulverized, pyrolyzed, and washed in a base solution followed by an acid solution to remove residual ash. SEM imaging and BET surface area measurements are used to characterize the coal. The purified coal char is mixed into a slurry of coal char, Super P binder, and dimethylformamide, then applied on a stainless-steel plate to create supercapacitor electrodes. Three-electrode open-cell electrochemical measurements are used to characterize the supercapacitor performance of the coal char in varying electrolyte solutions using a Gamry Interface 1000E potentiostat. The different electrolytes explored include: aqueous acid 0.5 M H2SO4, aqueous base 6 M KOH, and aqueous neutral solutions 0.5 M Na2SO4, 4 M LiNO3, water-in-salt electrolyte using 12.5 M NaClO4, . Voltage range, specific capacitance, electrochemical impedance, and charge-discharge characteristics of the coal char in the different electrolytes are characterized by cyclic voltammetry, chronopotentiometry, and electrochemical impedance spectroscopy measurements. The results provide important insight into the optimal electrolyte composition for use with coal char supercapacitor electrodes, and contribute to current understanding of electrode-electrolyte interactions in carbon supercapacitors.
This work is supported in-part by NSF Award #1742696.
Reference
1.Rakesh Kumar Gupta, Mukul Dubey, Parashu Kharel, Zhengrong Gu, Qi Hua Fan, Biochar activated by oxygen plasma for supercapacitors, Journal of Power Sources, Volume 274, 2015, Pages 1300-1305.
2. H. H. Schobert, Coal; The Energy Source of the Past and Future, pg. 9, American Chemical Society, Washington (1987).

Figure 1
The Green Electrochemical Synthesis of Periodates and Application in API Synthesis
Authors: Waldvogel Siegfried R , Arndt Sebastian 
Published: July 2021

Periodates represent one of the most powerful and versatile oxidizers for organic synthesis. Common ways to generate it electrochemically employ lead dioxide anodes. The disintegration of these electrodes cause contaminations which impede sensitive applications.[1] The purification of periodates makes this reagent usually too costly pharmaceutical applications. With the use of boron-doped diamond a direct conversion of the inexpensive sodium and potassium iodide within an eight-electron oxidation process renders periodate. The novel process is scalable, heavy metal-free and can be conducted in batch as well as flow electrolyzers.[2] This approach can also be used for the regeneration of periodates from iodates. The process was implemented in a new synthetic approach to levetiracetam, which demonstrates the technical application and recycling of iodates in API synthesis.[3] The reactor concepts for the efficient preparation of multi-kg quantities will be presented.
References:
[1] D. Pollok, S. R. Waldvogel, Chem. Sci. 11 (2020) 12375–12592.
[2] S. Arndt, D. Weis, K. Donsbach, S. R. Waldvogel, Angew. Chem. Int. Ed.
132
,
(2020) 8112-8118.
[3] S. Arndt, B. Grill, H. Schwab, G. Steinkellner, U. Pogorevčnik, D. Weis, A. M. Nauth, T. Opatz, K. Donsbach, S. R. Waldvogel, M. Winkler, Green Chem.
(
2020), accepted.
Modelling Diffusion at Random Arrays of Active Sites: Revisiting the Voronoi Tessellation Concept
Authors: Pireddu Giovanni , Svir Irina , Amatore Christian , Oleinick Alexander 
Published: July 2021

Many practical systems at micro- and nanoscale can be represented as arrays of active sites distributed randomly [1]. As shown previously these systems can be efficiently addressed theoretically by using Voronoi diagrams [2, 3] which allows facile tessellation of the system into the unit cells around each active sites. The overall current flowing in the system can then be evaluated by modelling diffusion-reaction processes inside every unit cell and summing the contributions from individual active sites. Although this approach is tempting by its simplicity and efficiency [3] one should bear in mind that Voronoi diagram representing the unit cells by polygonal prisms remains approximation and as each approximation remains valid only under certain conditions. In this work [4] we show that even for the case of diffusion limited electron transfer (ET) the actual shapes of the unit cells are more complicated and depend on the local configuration of the neighbouring active sites. This was exemplified on the small patches of the random arrays with band-like and disk-like active sites via simulations and in the case of band-like active sites confirmed by analytical derivations.
Importantly, by comparing the total array current obtained by employing Voronoi tessellation and simulation of the system without any approximations we found that they agree well (relative error ca. 5% or less). At the same time, the individual contributions from the active sites are reproduced with a much larger relative error [4]. The latter suggests that in the case of kinetic control or reaction mechanisms that are more complicated than simple ET the diffusion-reaction competition between the active sites may become even stronger eventually leading to significant deviations from the total current predicted on the basis of the Voronoi approximation. This is currently investigated in our team.

Fig. 1. Comparison between the Voronoi tessellation boundaries (white dashed lines) and the actual boundaries (coloured surface) of the unit cells. Three disk-type active sites are shown as white disks.

References

[1] O. Sliusarenko, A. Oleinick, I. Svir, C. Amatore. J. Electrochem. Soc. 167, 2020, 013530.
[2] T. J. Davies and R. G. Compton. J. Electroanal. Chem. 585, 2005, 63.
[3] O. Sliusarenko, A. Oleinick, I. Svir, C. Amatore. ChemElectroChem 2, 2015, 1279.
[4] G. Pireddu, I. Svir, A. Oleinick, C. Amatore, Electrochim. Acta 365, 2020, 137338.

Figure 1
Nanoscale Electrochemistry Study Using SECCM Option of Park Systems
Authors: Zhang Jiali , Kim Byong 
Published: July 2021

Scanning electrochemical cell microscopy (SECCM) is a nanoelectrochemical scanning probe technique that creates a confined electrochemical cell (droplet) via meniscus contacting the surface by employing an electrolyte filled micropipette containing quasi-reference counter electrode(QRCE).[1] It is particularly useful to investigate the heterogeneity, or local electrochemical properties of the electrode surfaces by direct mapping the electroactivity with nanoscale resolution.
In this study, the electrochemically reversible [Ru (NH3)6]3+/2+ electron transfer process at a highly ordered pyrolytic graphite (HOPG) surface was recorded using Park NX12 AFM system. A single barrel glass nanopipette with Ag/AgCl inserted as QRCE was utilized. Using previous successful experience in commercializing pipette-based electrochemical microscopy,[2] Park Systems’ hardware and software enables localized nanoscopic cyclic voltammetry measurements conducted at each pixel each time the meniscus contacts the surface. Thus, a spatially resolved surface electroactivity mapping of HOPG at various scan rates were created with high-throughput at the micro-/nanoscale. The difference in electrochemical activity measured at the edge plane relative to the basal plane surface was shown.
This work demonstrates that Park Systems’ commercial SECCM option is promising for quantitative electroanalysis at the nanoscale, with potential applications in energy storage (battery) studies and corrosion research.

[1] Gao, R., Edwards, M. A., Qiu, Y., Barman, K., & White, H. S. (2020). Visualization of Hydrogen Evolution at Individual Platinum Nanoparticles at a Buried Interface. Journal of the American Chemical Society.

[2] Shi, W., Goo, D., Jung, G., Pascual, G., Kim, B., & Lee, K. Simultaneous Topographical and Electrochemical Mapping using Scanning Ion Conductance Microscopy–Scanning Electrochemical Microscopy (SICM-SECM).

Figure 1
Enabling Real-Time Quantification of Electrochemical Desorptionphenomena with Sub-Monolayer Sensitivity
Authors: Cavalca Filippo , Scott Søren 
Published: July 2021

Across many scientific and industrial fields, it is a challenge to analyze chemical reaction products with high sensitivity and fast time-response. This is especially true in systems related to electrochemical energy conversion and storage, such as batteries and fuel cells, where accurate monitoring of fast and transient reaction phenomena often reveals key insights.
Here, we present a unique analysis instrument using a microchip-based inlet system to couple a mass spectrometer directly to any liquid test environment, aqueous or non-aqueous, and exhibits a sensitivity up to 2-3 orders of magnitude than conventional differential electrochemical mass spectrometry (DEMS).(1–3) The instrument allows to measure the evolution of volatile products and consumption of reactants at electrode surfaces. Due to its extraordinary sensitivity, the system can measure all the individual volatile molecules desorbing from an electrode surface during a single electrochemical turnover. Product formation can be measured from total Faradaic currents of 1 mA all the way down to 200 nA, corresponding to approximately 0.2% of a monolayer (ML) desorbing from the electrode surface in 1s. These features enable time-resolved, fully quantitative measurements of transient phenomena during electrochemistry, providing fundamental insight in the electrochemical reaction mechanisms. Furthermore, an accurately calibrated on-chip gas system allows rapid gas switching between different gases, both inert and reactive. Due to the near-instantaneous equilibration between gas and electrolyte, the transient response of electrodes to rapid gas exposure changes can be measured.
As direct evidence of the ultrahigh sensitivity, i
n situ quantification the anodic desorption of less than ~1% of a ML of hydrogen on a Cu electrode in alkaline electrolyte (Fig. 1) is shown.(4) Finally, several examples of quantitative electrochemical measurements will be presented, including lattice oxygen contribution during OER on NiFeOxHy,(2) and hydrocarbon oxidation of propene on palladium. (3, 5)
Fig.1 H2 desorption on Cu(pc) in 0.1 M KOH.
(4)

D. B. Trimarco et al., Electrochim. Acta. 268, 520–530 (2018).

C. Roy et al., Nat. Catal.
1, 820–829 (2018).

A. Winiwarter et al., Energy Environ. Sci.
12, 1055–1067 (2019).

S. B. Scott et al., Catal. Sci. Technol. (2020).

A. Winiwarter et al., ChemElectroChem, in press.

Figure 1
Cation Co-Adsorption and Island Formation in the Electrochemical Environment
Authors: McCrum Ian T. , Koper Marc 
Published: July 2021

The electrode/electrolyte interface is complex, and its composition, structure, and dynamics affect the rate and mechanism of electrocatalytic reactions. The presence of spectator cations near the electrode surface, for example, is well known to affect the rate and selectivity of carbon dioxide electroreduction, where changing from a lithium to a cesium cation can increase the selectivity of ethylene production on copper from 2% to 31% [1]. While many explanations of the mechanism of the effect of these alkali metal cations has been proposed, no one theory has been well accepted. In previous work, we have shown that alkali metal cations can sit close to an electrode surface, in particular at high pH and low potentials; further, once close to (“adsorbed” on) the surface, these spectator cations can then interact with and alter the adsorption energy of reactive intermediates, such as those present during CO2 electroreduction [2], or adsorbed hydroxide (OH*) on platinum (an intermediate in many electrochemical reactions) [3]. In this work, we find a cation which when present in an alkaline electrolyte has a large effect on the binding strength of hydroxide (larger than that of the alkali metal cations) on a Pt(111) electrode and causes a significant hysteresis in hydroxide adsorption/desorption. Using a combination of detailed experiments on a single crystal Pt(111) electrode and density functional theory simulations, we show that this hysteresis results from the co-adsorption of the cation and of hydroxide, with an interaction between the cation and hydroxide which is so strong that it drives island formation and a first order phase transition in the OH* adlayer. This provides direct evidence for cation (co)adsorption. Implications for electrocatalysis and electrolyte design will be discussed.
[1] M.R. Singh, Y. Kwon, Y. Lum, J.W. Ager III, A.T. Bell, J. Am. Chem. Soc.,
138, 13006-13012 (2016).
[2] S.A. Akhade, I.T. McCrum, M.J. Janik, J. Electrochem. Soc., 163, F477 (2016).
[3] I.T. McCrum, M.J. Janik, J. Phys. Chem. C, 120, 1, 457-471 (2016).