bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Printing 3D Gel Polymer Electrolyte in Li-Ion Microbattery Using Stereolithography
Authors: Chen Qiming , Xu Rong , He Zitao , Zhao Kejie , Pan Liang 
Published: February 2020

3D li-ion microbattery has gained an increasing importance since the development of microelectromechanical systems (MEMS). Compared with the limited areal capacity for thin-film microbattery, 3D microbattery has the advantage of fully utilizing the limited footprint area without sacrificing the power density. Most of the 3D microbatteries that have been published nowadays require the a) patterning and/or depositing process to define the 3D electrode’s architecture and b) sealing case to ensure the encapsulation for liquid electrolyte. These process increase the difficulty to manufacture 3D microbatteries.
UV-curable gel polymer electrolyte (GPE) is one of the routes for creating low-cost, high-yield 3D microbatteries. By using the micro-stereolithography system, GPE can be built into different 3D shapes. Poly (ethylene oxide) (PEO) has been used as the polymer host in the polymer electrolyte. By incorporating lithium salt and organic solvents as plasticizers into the PEO host, a stable and high-conductivity gel electrolyte can be formed. The GPE combines the mechanical properties of a swollen polymer network with the high ion conductivity of the liquid electrolyte.
Here we demonstrated a method to manufacture 3D gel polymer electrolyte for microbattery. We characterized the GPE membrane by Electrochemical Impedance Spectroscopy (EIS). The result shows a promising ionic conductivity for the use of solid-state li-ion battery. A half-cell has also been assembled for studying the GPE’s cycle performance. The GPE is then fabricated by stereolithography into different 3D structures. SEM picture shows a nano-porous structure in GPE which facilitates the ion transportation. Assembled with electrode material and current collector, the 3D GPE can be built into a 3D microbattery. The microbattery shows a successful operation for 2 cycles, with a capacity of 1.4mAh cm2.
Voltage Charging Gold-Microtube Membranes for Electroporation
Authors: Martin Charles R , Experton Juliette , Wilson Aaron G. 
Published: February 2020

Electroporation of cell membrane occurs when sufficiently large electric field gradients (in the order of kV/cm) are applied to a cell medium. This is routinely accomplished in medicine and biology using voltage pulses above 1 kV in order to incorporate foreign molecules and genes into living cells.1 However, transient pore formation or reversible electroporation is a challenge with such large voltages because of Joule heating, pH changes and ion dissolution that lead to high cell mortality.2 Furthermore, special safety precautions are required. As such, the miniaturization of electroporation devices has been a research interest in order to reach similar electric field gradients with lower voltages.3 It was also shown that these microscopic devices result in higher electroporation yields and better cell viability, although often reducing the cell throughput.
We have developed an electroporation system that consists on charging gold microtubes inside a filter membrane to electroporate Escherichia coli at low voltages (<5 V).4 Supporting our experimental results with theoretical simulations, we have shown that electric field gradients of 4 kV/cm, sufficiently large to reversibly porate the bacteria membrane, were formed inside the gold microtubes. Following the incorporation of exogenous probes inside E. coli with fluorescence microscopy and spectroscopy, we have determined that up to 40% of the bacteria were reversibly electroporated. This is more than an order of magnitude higher than the efficiency obtained with a commercial electroporation device. Finally, cell throughput of >30 million cells per minutes, higher than any previously reported device, were obtained.

Gehl, J. Acta Physiol. Scand.
2003, 177, 437-447.

Lee, W. G.; Demirci, U.; Khademhosseini, A. Integr. Biol.
2009, 1, 242-251.

Geng, T.; Lu, C. Lab Chip
2013, 13, 3803-3821.

Experton, J.; Wilson, A. G.; Martin C. R. Anal. Chem. [Article ASAP]. DOI: 10.1021/acs.analchem.6b03820. Published Online: Nov 17, 2016.
(Invited) Datahub for Energy Materials Network
Authors: Sivaraman Chitra , Macduff Matt 
Published: February 2020

This talk will provide an overview of the DataHUB being built for the U.S. Department of Energy’s Energy Materials Network (EMN). The DataHUB will be a best-in-class data-serving infrastructure, leveraging standard practices to collect, manage, and curate data to accelerate the process of materials discovery, characterization, and commercial deployment of technologies. It will provide open, uninterrupted, easy, and secure access to codes, models, experiments, simulated data, and journal publications produced by all projects within the EMN consortia. A central repository currently does not exist for the EMN projects and studies. Rather, the data are being stored by the principal investigators at their home institutions and are not easily accessible by other users. Moreover, the information is vulnerable to loss, while the opportunities for cross-cutting integration are, at best, limited. By creating a central hub for data storage, discovery, and access, potential duplication of experiments and studies along with other efforts that could delay scientific progress can be avoided. The DataHUB’s short-term objective will be to provide this repository service for data produced by the EMN consortia. The central hub will allow consortia members to focus on the science, research, and analysis while the DataHUB will maintain data security and access, as well as offer a standardized approach to curate the data. The DataHUB will provide autonomy to each consortium for creating the content of the portal and tools for their specific projects. In addition, the DataHUB will be extended to enable seamless integration of multidisciplinary scientific investigations and analyses to address common material challenges spanning all EMNs.
Tetranitrocalix[4]Arene Tetraradical Tetraanion As an Electrochemically Generated Ligand
Authors: Ludvík Jiří , Liška Alan , Vojtíšek Pavel 
Published: February 2020

A tetraradical tetraanion is a stable product of 4-electron reduction of cone-5,11,17,23-tetranitro-25,26,27,28-tetrapropoxycalix[4]arene in nonaqueous dimethyl-formamide (DMF) [1]. It represents an electrochemically generated ligand which is able to coordinate all alkali metal ions. The existence of these complexes was recently proved by DC-polarography, cyclic voltammetry and UV-VIS spectroelectrochemistry. Observed stoichiometries are 2:1 (for Li+, Na+, Cs+), 3:1 (Rb+, Cs+) and 4:1 (K+). The complexes are kinetic labile and they have character of ion pairs between negatively charged nitroradical group and metal cations. The „normalized“ values of the stability constants were compared with stability constants of ionic pairs of alkali metals with nitrite anions. About three orders higher values for calix[4]arene radicals can be explained by a „structural vector“. Four charged and oriented nitroradicals on calix-scaffold as donor groups form considerably higher „field for electrostatic interaction“ than randomly oriented simple anions. The same type of interaction was revealed also for cone-5,11,17,23-tetranitro-25,26,27,28-tetrakis(ethoxycarbonylmethoxy)calix[4]arene. This compound was originally suspicious of binding alkali metal ions by ester groups on the lower rim, however, the experimental data exclude this possibility.
Reference
[1] A. Liška, P. Vojtíšek, A.J. Fry, J. Ludvík, Electrochemical and Quantum Chemical Investigation of Tetranitrocalix[4]arenes: Molecules with Multiple Redox Centers, J. Org. Chem. 78 (2013) 10651-10656.
Trifecta of Ionic Liquid As Solvent, Electrolyte, and Mediator
Authors: Shimakoshi Hisashi , Takamatsu Kanako , Hisaeda Yoshio 
Published: February 2020

In recent years, ionic liquids have been the subject of considerable interest as promising media for chemical reactions including of electroorganic synthesis because of their unique characteristics such as low melting point, negligible vapor pressure, non-flammability, high conductivity and the good solubility of many organic and inorganic compounds as well as biomaterials.1 In the development of ionic liquid study, here we reported the synthesis of redox active ionic liquids, such as 1-ethyl-4-(methoxycarbonyl)pyridinium bis(trifluoromethanesulfonyl)amide (P1
•
TFSA) and 1-ethyl-3-(ethoxycarbonyl)pyridinium bis(trifluoromethanesulfonyl)amide (m3
•
TFSA). These redox active ionic liquids were synthesized from its iodide form by anion exchange reaction and were characterized by NMR, UV-VIS, IR and elemental analyses. These compounds showed redox waves around -0.6~-1.5 V vs. Ag/AgCl and were worked as electron mediator for the electroorganic reaction (Figure 1).

References

1) J. P. Hallett, T. Welton, Chem. Rev.
2011, 111, 3508.

Figure 1
Mechanistic Insight into the Electrocatalytic Hydrogenation and Electroreduction of Furfural
Authors: Chadderdon Xiaotong , Chadderdon David J , Matthiesen John Edward , Tessonnier Jean-Philippe , Li Wenzhen 
Published: February 2020

Electrochemical reduction of biomass-derived platform chemicals is an emerging route for biofuels and chemicals production, where renewable electricity drives reactions on electrodes without the need for external hydrogen supply.1-3 However, the mechanisms governing electrochemical reduction of biomass-derived furanic compounds and its competition with hydrogen evolution reaction (HER) remain unclear. In this talk, we investigate the electrochemical reduction of furfural on copper electrodes for the production of 2-methylfuran (an important potential biofuel additive), furfuryl alcohol (a valuable chemical building block), and dimerization products. Through novel electrochemical techniques, we distinguish between two mechanisms – electrocatalytic hydrogenation (ECH) and outer-sphere electroreduction (ER). Understanding of the underlying mechanisms enables us to tune product selectivity and the competition between ECH, ER, and HER by varying reaction conditions including cathode potential, initial furfural concentration and electrolyte pH. Cyclic voltammetry and bulk electrolysis results clarify the reaction pathways of 2-methylfuran and furfuryl alcohol formation under these conditions. We demonstrate that electrochemical reduction is a promising route for selective furfural conversion and highlight the importance of the underlying mechanisms. These findings can be applied to related biomass-derived platform chemicals including 5-(hydroxymethyl)furfural and other carbonyl-containing compounds.
References:
1. Xin, L.; Zhang, Z.; Qi, J.; Chadderdon, D. J.; Qiu, Y.; Warsko, K. M.; Li, W., Electricity storage in biofuels: selective electrocatalytic reduction of levulinic acid to valeric acid or gamma-valerolactone. ChemSusChem
2013, 6, 674–686.
2. Matthiesen, J. E.; Suástegui, M.; Wu, Y.; Viswanathan, M.; Qu, Y.; Cao, M.; Rodriguez-Quiroz, N.; Okerland, A.; Kraus, G.; Raman, D. Raj; Shao, Z.; Tessonnier, J.-P., Electrochemical Conversion of Biologically Produced Muconic Acid: Key Considerations for Scale-Up and Corresponding Technoeconomic Analysis. ACS Sustainable Chem. Eng.
2016, 4, 7098–7109.
3. Suástegui, M.; Matthiesen, J. E.; Carraher, J. M.; Rodriguez Quiroz, N.; Okerlund, A.; Cochran, E. W.; Shao, Z.; Tessonnier, J.-P., Combining Metabolic Engineering and Electrocatalysis: Application to the Production of Polyamides from Sugar. Angew. Chem. Int. Ed.
2016, 55, 2368–2373.
Understanding the Metabolic Activation of Therapeutic Agents with Molecular Electrochemistry: The Example of Metallocifen Anti-Cancer Drug Canditates
Authors: Amatore Christian Andre , Buriez Olivier , Labbe Eric 
Published: February 2020

Organometallic chemistry has allowed the design and emergence of a new class of metal-based bioactive molecules and a variety of drugs already used or being tested against cancer. In this field, cisplatin is well-known and widely used clinically. However, recent contributions are focusing on the functionalization of clinically validated purely organic drugs with complexes derivatized by a metallocene group. This approach has been shown to exalt the anti-cancer properties of the organic moiety, and has been successfully used to design ferrocifens. These complexes involve a ferrocenyl group covalently grafted onto the tamoxifen skeleton, the current gold standard for endocrine breast cancer therapy. Based on the same strategy, several original ruthenocene- and osmocene-tamoxifen derivatives have been recently synthesized and were also successfully tested against breast and other cancer cells.
This communication will detail how the development of such potent metallodrugs was directly bearing on the accurate mechanistic understanding of their electron transfer activation provided by the synergistic combination of molecular electrochemistry and biological approaches.
Photobioelectrochemistry of Intact Chloroplasts for Solar Energy Conversion
Authors: Hasan Kamrul , Milton Ross D , Grattieri Matteo , Minteer Shelley D. 
Published: February 2020

Solar energy is a highly exploitable energy source for renewable energy technologies; thus, a great deal of recent research has focused on the ability to generate electrical energy from solar energy (photoelectrochemistry). This has resulted in a wide variety of photoactive biomaterials being studied at electrode surfaces, such as isolated photosystems, thylakoid membranes as well intact photosynthetic organisms.
Chloroplasts are photosynthetic organelles that harness solar energy in higher plants and algae. They are the vital sources of carbon-based fuels and have self-repair mechanisms against photo-damage; however, chloroplasts are less studied for harnessing solar energy. The electrochemical communication of chloroplasts at electrode surfaces is challenging since they are shielded inside thick electrochemically-insulating cell membranes. Therefore, the majority of studies surrounding chloroplasts in photobioelectrochemical systems (PBESs) utilize soluble exogenous electron transfer (ET) mediators. The use of soluble electron mediators, however, is not feasible for large-scale application.
Redox polymers are polymeric backbones that have been modified with redox-active moieties and can be used as an immobilization matrix as well as a non-diffusive electron mediator for extracellular-ET from biomaterials to the electrode. Nevertheless, a successful electrochemical study on chloroplasts with any redox polymer is yet to be reported. Here, we report the photoelectrochemical wiring of chloroplasts on a naphthoquinone-based redox polymer. Intact chloroplasts were immobilized on Toray carbon paper electrodes and illuminated under a fiber optic light to simulate sunlight. Cyclic voltammetric and amperometric experiments demonstrate the ability to obtain photo-excited electrons that are produced from water oxidation by intact chloroplasts. In the presence of a diffusive mediator as well as the redox polymer, maximum photobiocurrents obtained from the chloroplasts are as high as 28±5 µA cm-2.
Biological Power Sources Based on Transparent and Capacitive Electrodes
Authors: González-Arribas Elena , Aleksejeva Olga , Shleev Sergey 
Published: February 2020

Here we present fabrication and characterization of transparent biological power sources, specifically, both conventional and charge-storing bio-fuel and bio-solar cells. The biodevices are built on different transparent conductors – metal and oxide-, viz. gold and indium tin oxide. Transparency is a relevant feature to take into account when developing power sources for certain potential applications. However, most of designed biological power sources described in the literature are opaque.
Bio-fuel cells are suitable power sources to implement in electronic contact lenses. The power needed for smart lenses is generated by converting in situ available chemical energy from different biofuels presented in human tears into electric energy. Here we show different approaches that our group has developed to design high performing and transparent conventional enzymatic fuel cells [1] and self-charging chemical biosupercapacitors [2, 3] for contact lens application (Fig. 1A).
Bio-solar cells, i.e. devices based on biocatalysts, which can directly transform solar energy into electric energy, are in the spotlight nowadays. Here we show the very first solar biosupercapacitor (Fig. 1B), which is built from transparent and nanostructured, i.e. highly capacitive, indium tin oxide based electrodes [4]. The biodevice is able to convert solar energy into electric energy, which is capacitively stored within the same volume used for conversion. The solar biosupercapacitor, consisting of thylakoid membrane modified anode and bilirubin oxidase modified cathode ionically coupled in a closed system at neutral pH, is charged by the ambient daylight. Because of the materials used, the resulting biodevice is a simple to build, inexpensive, and sustainable power source for low-power low-voltage electronics.
Fig. 1. Transparent biological power sources.
(A) Charge-storing glucose/oxygen fuel cell. (B) Self-charging solar biosupercapacitor.
This work has been financially supported by the European Commission (PEOPLE-2013-ITN-607793).
1. D. Pankratov, R. Sundberg, J. Sotres, I. Maximov, M. Graczyk, D.B. Suyatin, E. González-Arribas, A. Lipkin, L. Montelius, S. Shleev, Journal of Power Sources, 2015, 294, 501.
2. D. Pankratov, E. González-Arribas, Z. Blum, S. Shleev, Electroanalysis, 2016, 28, 1250.
3. E. González-Arribas, D. Pankratov, G. Sébastien, N. Mano, Z. Blum, S. Shleev, Electroanalysis, 2016, 28, 1290.
4. E. González-Arribas, O. Aleksejeva, T. Bobrowski, M.D. Toscano, L. Gorton, W. Schuhmann, S. Shleev, Electrochemistry Communications, 2017, 74, 9.

Figure 1
Nanocrystalline Co3-XNixO4 with Low Ni Concentration: Enhanced Oxygen Evolution Activity Compared to Co3O4
Authors: Singhal Aditi , Bisth Anuj 
Published: February 2020

Nano-crystalline Co3O4 and a series of Ni-doped Co3O4; Co3-xNixO4 (0.0075 £ x £ 0.30) have been synthesized using solution combustion method. Complete characterization is carried out using XRD, TEM and BET surface area analysis. XRD shows pure nano-crystalline phase of Co3O4 with no peaks related to Ni or nickel oxide confirming that Ni is not present as a separated phase on the surface and has been substituted in the lattice. TEM studies for as prepared samples (400 oC) show that particles of 0.5% Ni doped Co3O4 (Co2.985Ni0.015O4) are around 60 nm in size. Calcination of Co2.985Ni0.015O4 at 600 °C for 10 hours results into well-defined hexagonal morphology which could be seen both by TEM and SEM. After calcination, particle size becomes 70 nm. Estimated BET surface area for Co2.985Ni0.015O4 (calcined at 600°C) is 10m2/g.
Detailed electrochemical studies have been carried out in basic, neutral buffer and neutral electrolyte medium. Both Co3O4 and Co3-xNixO4 were found active for oxygen evolution reaction (OER) with an interesting behavior in doped compound. It is found that lower nickel doping significantly enhances the OER activity in all the mediums; basic, neutral and neutral buffer. Figure 1 depicts that just 0.5% Ni-doped Co3O4 (Co2.985Ni0.015O4) is far more active than Co3O4 both in terms of current density and onset potential in K2SO4 medium. This enhancement nevertheless decreases once the doping concentration reaches beyond 0.5%. Figure 2 shows that OER activity (chronoamperomertic current) of Co3O4 increases after 0.25% Ni doping peaking at 0.5% and thereafter the reduction in the activity takes place. 1% Ni doped Co3O4 is less active than 0.25% Ni doped Co3O4. Once the doping concentration is 2.5% there is no enhancement in the activity compared to Co3O4. In the same way no effect is seen at 5 and 10% doping of Ni and the activity is similar to parent Co3O4. Same trend is observed in all other medium. Interestingly, in phosphate buffer solution (PBS) Co3O4 and 0.5% Ni-doped Co3O4 show OER at near thermodynamic potential i.e at a very low over potential. Similar effect was observed by Nocera and co-workers on cobalt oxide 1-2. This conclusively states that Co3O4 and its doped variant form similar type of in situ active sites as noticed Nocera and co-workers.

References : 1. M.W. Kanan, D.G. Nocera, Science 321 (2008) 1072-1075. 2. Y. Surendranath, M.W. Kanan, D.G. Nocera, Journal of the American Chemical Society 132 (2010) 16501-16509

Figure 1
(Invited) Evidence for Magnetic Effects on Electron Transfer
Authors: Lee Heung Chan , Gellett Wayne L. , Minteer Shelley D. , Knoche Krysti L. , Rathuwadu Nadeesha , Leddy Johna 
Published: February 2020

Electron transfer events are commonly considered in light of the transfer of charge. But, electrons also have properties of spin. Here, various systems are evaluated for impact of spin on rates of electron transfer. Literature and experimental data are considered. Electron spins interact with magnetic fields. In our experimental studies, magnetic microparticles are introduced to the electrode surface.
From the literature, correlations between measured parameters and magnetic properties of electrodes and electroactive species are presented. This includes rate constants for heterogeneous and homogeneous electron transfer.
From laboratory studies with micromagnets held to the electrode with a Nafion coating, impacts on homogeneous and heterogeneous electron transfer are found.

For transition metal complexes such as M(bpy)₃z+ present at near contact in Nafion, electron hopping rates are measured as self exchange rates, k₁₁. When compared to simple Nafion films, rates of electron electron hopping are enhanced in the presence of magnets; effects scale with the number of spin (unpaired electrons) involved in the reaction. Temperature studies chart variation in the energy of activation (reorganization energy) and the pre-exponential factor.

For adsorbate reactions, magnetic effects are substantial for reactions such as CO oxidation and hydride formation on palladium. Rates are enhanced > 100 fold.

Hydrogen evolution reaction (HER) rates for poorly electrocatalytic electrodes are enhanced substantially on introduction of micromagnets.

Because transfer of electrons requires transfer of both charge and spin, electron transfer rates can be slowed when rates of spin transfer are slow. Facilitating rates of spin transfer as by introduction of micromagnets increases rates of electron transfer reactions.