Electrochemical decontamination of titanium dental implants. An in vitro biofilm model study.

OBJECTIVES: The objective of this study is to study the effect of electrochemical treatment on biofilms developed on titanium dental implants, using a six-species in vitro model simulating subgingival oral biofilms. MATERIALS AND METHODS: Direct electrical current (DC) of 0.75 V, 1.5 V, and 3 V (anodic polarization, oxidation processes) and of -0.75 V, -1.5 V, and -3 V (cathodic polarization, reduction processes) was applied between the working and the reference electrodes for 5 min on titanium dental implants, which have been previously inoculated with a multispecies biofilm. This electrical application consisted of a three-electrode system where the implant was the working electrode, a platinum mesh was the counter electrode, and an Ag/AgCl electrode was the reference. The effect of the electrical application on the biofilm structure and bacterial composition was evaluated by scanning electron microscopy and quantitative polymerase chain reaction. A generalized linear model was applied to study the bactericidal effect of the proposed treatment. RESULTS: The electrochemical construct at 3 V and -3 V settings significantly reduced total bacterial counts (p < .05) from 3.15 × 106 to 1.85 × 105 and 2.92 × 104 live bacteria/mL, respectively. Fusobacterium nucleatum was the most affected species in terms of reduction in concentration. The 0.75 V and -0.75 V treatments had no effect on the biofilm. CONCLUSION: Electrochemical treatments had a bactericidal effect on this multispecies subgingival in vitro biofilm model, being the reduction more effective than the oxidative treatment.

Stress induced by crude glycerol in a thermophilic digester: microbial community divergence and resilience, but slow process recovery.

Recovery from stress is an important property for anaerobic digestion (AD). Although AD is quite adaptable with regard to waste composition, new substrates added to stable systems may cause process decline. We tested whether crude glycerol would cause stress to a thermophilic AD microbiome previously stabilized long-term on a low C/N ratio feedstock. Three-percent (v/v) crude glycerol was added to the basal substrate (poultry litter) for two hydraulic retention time (HRT) periods. This caused stress where biogas volume and methane percentage dramatically decreased and VFA levels increased. When the basal substrate was resumed, secondary inhibition occurred, resulting in even greater stress (biogas production ceased, methane 3.6%). Unassisted recovery of system processes required eight HRT periods. In contrast, crude glycerol applied at a lower organic loading rate did not cause inhibition. Crude glycerol caused changes in dominance in the microbial community (16S rRNA pyrotags). Although process resilience was slow, the recovery of digester functions occurred in conjunction with the recovery of community structure, particularly putative syntrophic acetate-oxidizing bacteria. KEY POINTS: • Crude glycerol caused stress in thermophilic co-digestion with poultry litter. • Unassisted resilience of digester functions (methane) required 8 HRT. • Syntrophic acetate-oxidizing bacteria implicated for keystone resilience functions. Graphical abstract.

A Membrane-Free Redox Flow Battery with Two Immiscible Redox Electrolytes.

Flexible and scalable energy storage solutions are necessary for mitigating fluctuations of renewable energy sources. The main advantage of redox flow batteries is their ability to decouple power and energy. However, they present some limitations including poor performance, short-lifetimes, and expensive ion-selective membranes as well as high price, toxicity, and scarcity of vanadium compounds. We report a membrane-free battery that relies on the immiscibility of redox electrolytes and where vanadium is replaced by organic molecules. We show that the biphasic system formed by one acidic solution and one ionic liquid, both containing quinoyl species, behaves as a reversible battery without any membrane. This proof-of-concept of a membrane-free battery has an open circuit voltage of 1.4 V with a high theoretical energy density of 22.5 Wh L-1 , and is able to deliver 90 % of its theoretical capacity while showing excellent long-term performance (coulombic efficiency of 100 % and energy efficiency of 70 %).

New Operational Modes to Increase Energy Efficiency in Capacitive Deionization Systems.

In order for capacitive deionization (CDI) as a water treatment technology to achieve commercial success, substantial improvements in the operational aspects of the system should be improved in order to efficiently recover the energy stored during the deionization step. In the present work, to increase the energy efficiency of the adsorption-desorption processes, we propose a new operational procedure that utilizes a concentrated brine stream as a washing solution during regeneration. Using this approach, we demonstrate that by replacing the electrolyte during regeneration for a solution with higher conductivity, it is possible to substantially increase round-trip energy efficiency. This procedure was experimentally verified in a flow cell reactor using a pair of carbon electrodes (10(2) cm geometric area) and NaCl solutions having concentrations between 50 and 350 mmol·L(-1). According to experimental data, this new operational mode allows for a better utilization of the three-dimensional structure of the porous material. This increases the energetic efficiency of the global CDI process to above 80% when deionization/regeneration currents ratio are optimized for brackish water treatment.

Tuning mono-divalent cation water composition by the capacitive ion-exchange mechanism.

Soil salinization poses a significant challenge to agricultural activities. To address this, the agricultural industry seeks an irrigation water solution that reduces both ionic conductivity and sodium adsorption rate (SAR), thereby diminishing the risks of soil sodification and fostering sustainable crop production. Capacitive deionization (CDI) is an attractive electrochemical technology to advance this search. Recently, a one-dimensional transient CDI model unveiled a capacitive ion-exchange mechanism presenting the potential to adjust the treated water composition by modifying monovalent and divalent cation concentrations, thereby influencing the SAR index. This behavior would be achieved by using electrodes rich in surface functional groups able to efficiently capture divalent cations during conditioning and releasing them during charging while capturing monovalent ions. Beyond the theoretical modelling, the current experimental research demonstrates, for the first time, the effectiveness of the capacitive ion-exchange mechanism in a CDI pilot plant using real water samples spiked with solutions containing specific mono and divalent ions. Electrosorption experiments and computational modeling, specifically Density-Functional Theory (DFT), were used along with the analysis of the surface functional groups present in the electrodes to describe the capacitive ion-exchange phenomenon and validate the steps involved on it, highlighting the conditioning as a critical step. Various operational and flow modes confirm the versatility of CDI technology, achieving separation factors (RMg/Na) of 5-6 in batch, raising production from 0.5 to 0.8 L m-2 h-1 (batch) to 8.0-8.1 L m-2 h-1 when using single pass although reducing RMg/Na to 2. The reliability of the CDI technology in reducing SAR was also successfully tested with different influent compositions, including magnesium and calcium. Finally, the robustness of the capacitive ion-exchange mechanism was validated by a second CDI laboratory 9-cell stack cycled over 350 cycles. Our results confirm the reported theoretical model and expands the conclusions through the experiments in a pilot plant showing direct implications for employing CDI in agricultural applications.

Optimizing the energy efficiency of capacitive deionization reactors working under real-world conditions.

Capacitive deionization (CDI) is a rapidly emerging desalination technology that promises to deliver clean water while storing energy in the electrical double layer (EDL) near a charged surface in a capacitive format. Whereas most research in this subject area has been devoted to using CDI for removing salts, little attention has been paid to the energy storage aspect of the technology. However, it is energy storage that would allow this technology to compete with other desalination processes if this energy could be stored and reused efficiently. This requires that the operational aspects of CDI be optimized with respect to energy used both during the removal of ions as well as during the regeneration cycle. This translates into the fact that currents applied during deionization (charging the EDL) will be different from those used in regeneration (discharge). This paper provides a mechanistic analysis of CDI in terms of energy consumption and energy efficiencies during the charging and discharging of the system under several scenarios. In a previous study, we proposed an operational buffer mode in which an effective separation of deionization and regeneration steps would allow one to better define the energy balance of this CDI process. This paper reports on using this concept, for optimizing energy efficiency, as well as to improve upon the electro-adsorption of ions and system lifetime. Results obtained indicate that real-world operational modes of running CDI systems promote the development of new and unexpected behavior not previously found, mainly associated with the inhomogeneous distribution of ions across the structure of the electrodes.

New testing procedures of a capacitive deionization reactor.

Currently, according to conventional charge-discharge profiles, energy consumed in charging Capacitive Deionization (CDI) systems is always a function of different parameters (current used for charging, capacitance and current employed for discharging) making it difficult to separate the effect of these parameters on CDI performance and energy efficiency. Thus, energy efficiencies are strongly influenced by the current in the preceding charge or discharge stage of the process. We find consistently that this phenomenon, which to our knowledge has not been addressed in previous CDI communications, is much more intense when different currents are applied for each of the charging and discharging cycles. The investigation reported here provides a mechanistic analysis of the operational aspects of CDI and develops a new procedure that allows for a precise evaluation of performance and energy efficiency. Furthermore, the model developed here allows one to separate charge and discharge cycles, and therefore contributes to the possibility of defining an operational mode for real-world devices in which effective separation of deionization and regeneration steps needs to be implemented. This method of analysis could be useful not only for CDI but also for other electrochemical systems such as in secondary batteries and supercapacitors where charge and discharge are typically employed.

The redox mediated - scanning droplet cell system for evaluation of the solid electrolyte interphase in Li-ion batteries.

The so-called solid electrolyte interphase (SEI), a nanolayer formed on the negative electrode of lithium-ion batteries during the first cycles, largely influences some key performance indicators such as cycle life and specific power. The reason is due to the fact that the SEI prevents continuous electrolyte decomposition, making this protecting character extremely important. Herein, a specifically designed scanning droplet cell system (SDCS) is developed to study the protecting character of the SEI on lithium-ion battery (LIB) electrode materials. SDCS allows for automatized electrochemical measurements with improved reproducibility and time-saving experimentation. Besides the necessary adaptations for its implementation for non-aqueous batteries, a new operating mode, the so-called redox mediated-scanning droplet cell system (RM-SDCS), is established to investigate the SEI properties. By adding a redox mediator (e.g. a viologen derivative) to the electrolyte, evaluation of the protecting character of the SEI becomes accessible. Validation of the proposed methodology was performed using a model sample (Cu surface). Afterwards, RM-SDCS was employed on Si-graphite electrodes as a case study. On the one hand, the RM-SDCS shed light on the degradation mechanisms providing direct electrochemical evidence of the rupture of the SEI upon lithiation. On the other hand, the RM-SDCS was presented as an accelerated method capable of searching for electrolyte additives. The results indicate an enhancement in the protecting character of the SEI when 4 wt% of both vinyl carbonate and fluoroethylene carbonate were used simultaneously.

Daily Transfers, Archiving Populations, and Measuring Fitness in the Long-Term Evolution Experiment with Escherichia coli.

The Long-Term Evolution Experiment (LTEE) has followed twelve populations of Escherichia coli as they have adapted to a simple laboratory environment for more than 35 years and 77,000 bacterial generations. The setup and procedures used in the LTEE epitomize reliable and reproducible methods for studying microbial evolution. In this protocol, we first describe how the LTEE populations are transferred to fresh medium and cultured each day. Then, we describe how the LTEE populations are regularly checked for possible signs of contamination and archived to provide a permanent frozen "fossil record" for later study. Multiple safeguards included in these procedures are designed to prevent contamination, detect various problems when they occur, and recover from disruptions without appreciably setting back the progress of the experiment. One way that the overall tempo and character of evolutionary changes are monitored in the LTEE is by measuring the competitive fitness of populations and strains from the experiment. We describe how co-culture competition assays are conducted and provide both a spreadsheet and an R package (fitnessR) for calculating relative fitness from the results. Over the course of the LTEE, the behaviors of some populations have changed in interesting ways, and new technologies like whole-genome sequencing have provided additional avenues for investigating how the populations have evolved. We end by discussing how the original LTEE procedures have been updated to accommodate or take advantage of these changes. This protocol will be useful for researchers who use the LTEE as a model system for studying connections between evolution and genetics, molecular biology, systems biology, and ecology. More broadly, the LTEE provides a tried-and-true template for those who are beginning their own evolution experiments with new microbes, environments, and questions.

New Technique for Probing the Protecting Character of the Solid Electrolyte Interphase as a Critical but Elusive Property for Pursuing Long Cycle Life Lithium-Ion Batteries.

The formation of a protecting nanolayer, so-called solid electrolyte interphase (SEI), on the negative electrode of Li-ion batteries (LIBs) from product precipitation of the cathodic decomposition of the electrolyte is a blessing since the electrically insulating nature of this nanolayer protects the electrode surface, preventing continuous electrolyte decomposition and enabling the large nominal cell voltage of LIBs, e.g., 3.3-3.8 V. Thus, the protection performance of the nanolayer SEI is essential for LIBs to achieve a long cycle life. Unfortunately, the evaluation of this critical property of the SEI is not trivial. Herein, a new, cheap, and easily implementable methodology, the redox-mediated enhanced coulometry, is presented to estimate the protecting quality of the SEI. The key element of the methodology is the addition of a redox mediator in the electrolyte during the degassing step (after the SEI formation cycle). The redox mediator leads to an internal self-discharge process that is inversely proportional to the protecting character of the SEI. Also, the self-discharge process results in an easily measurable decrease in Coulombic efficiency. The influence of vinylene carbonate as an electrolyte additive in the resulting SEI is used as a case study to showcase the potential of the proposed methodology.

Macromolecular Engineering of Poly(catechol) Cathodes towards High-Performance Aqueous Zinc-Polymer Batteries.

Aqueous zinc-polymer batteries (AZPBs) comprising abundant Zn metal anode and redox-active polymer (RAP) cathodes can be a promising solution for accomplishing viable, safe and sustainable energy storage systems. Though a limited number of RAPs have been successfully applied as organic cathodes in AZPBs, their macromolecular engineering towards improving electrochemical performance is rarely considered. In this study, we systematically compare performance of AZPB comprising Zn metal anode and either poly(catechol) homopolymer (named P(4VC)) or poly(catechol) copolymer (named P(4VC86-stat-SS14)) as polymer cathodes. Sulfonate anionic pendants in copolymer not only rendered lower activation energy and higher rate constant, but also conferred lower charge-transfer resistance, as well as facilitated Zn2+ mobility and less diffusion-controlled current responses compared to its homopolymer analogue. Consequently, the Zn||P(4VC86-stat-SS14) full-cell exhibits enhanced gravimetric (180 versus 120 mAh g-1 at 30 mg cm-2) and areal capacity (5.4 versus 3.6 mAh cm-2 at 30 mg cm-2) values, as well as superior rate capability both at room temperature (149 versus 105 mAh g-1 at 150 C) and at -35 °C (101 versus 35 mAh g-1 at 30 C) compared to Zn||P(4VC)100. This overall improved performance for Zn||P(4VC86-stat-SS14) is highly encouraging from the perspective applying macromolecular engineering strategies and paves the way for the design of advanced high-performance metal-organic batteries.

An Exploratory Data Analysis on the Influence of Role Rotation in a Small-Sided Game on Young Soccer Players.

The aim of the present study was to analyze the behavior of players in a standard small-sided game (SSG) according to the role played (offensive (OF), defensive (DF), and wildcard (W)) and its relationship with physical demands (PHYD), technical performance (TP), and internal load (RPE). A total of 24 young highly trained male soccer players (under 16: n = 12; under 19: n = 12) participated. During the SSG, the players alternated the three roles (OF, DF, and W). The duration of each repetition was 4 min with a passive rest of 3 min between them. Furthermore, it emphasized the high demand in all defensive parameters. In addition, DF roles showed higher values in PHYD and RPE, followed by the OF roles, and finally by the W roles. A complementary, positive moderate correlation was found between PHYD and RPE in the U16 dataset (r = 0.45, p < 0.006). Very large positive correlations were also found between PHYD and RPE in the U19 and merged dataset (r = 0.78, p < 0.001 and r = 0.46, p < 0.63, respectively). This information could be useful for coaches in order to structure the roles in SSGs and control training load.

A critical perspective on rechargeable Al-ion battery technology.

The development of rechargeable aluminum-ion batteries (AIBs) has recently attracted much scientific attention due to the low cost and high specific capacity of Al. Most efforts are being concentrated on enhancing the specific charge capacity of active materials for the positive electrode, while other important issues for commercial deployment of this technology have often been overlooked. The aim of this frontier article is not to systematically review the recent advances in the literature, but to bring under the spotlight the critical aspects requiring intensive research activity for paving the way toward the commercialization of AIBs. After a brief revision of the fundaments of an Al-ion battery, the discussion is classified into 5 sections: energy density, specific power, cost, cycle life and safety. Finally, a performance comparison among Al-ion, Li-ion and lead-acid battery technologies on the basis of these 5 primary parameters summarizes the strengths and limitations of Al-ion batteries.

Exploring the Versatility of Membrane-Free Battery Concept Using Different Combinations of Immiscible Redox Electrolytes.

Lately, the field of redox flow batteries is flourishing because of the emergence of new redox chemistries, including organic compounds, new electrolytes, and innovative designs. Recently, we reported an original membrane-free battery concept based on the mutual immiscibility of an aqueous catholyte containing hydroquinone and an ionic liquid anolyte containing para-benzoquinone as redox species. Here, we investigate the versatility of this concept exploring the electrochemical performance of 10 redox electrolytes based on different solvents, such as propylene carbonate, 2-butanone, or neutral-pH media, and containing different redox organic molecules, such as 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine1-oxyl (OH-TEMPO), or substituted anthraquinones. The most representative electrolytes were paired and used as immiscible anolyte-catholyte in 5 different membrane-free batteries. Those batteries with substituted anthraquinones in the anolyte exhibited up to 50% improved open-circuit voltage (2.1 V), an operating voltage of 1.75 V, and 62% higher power density compared with our previous work. On the other hand, the partition coefficient of redox molecules between the two immiscible phases and the inherent self-discharge occurring at the interphase are revealed as intrinsic features affecting the performance of this type of membrane-free battery. It was successfully demonstrated that the functionalization of redox molecules is an interesting strategy to tune the partition coefficients mitigating the crossover that provokes low battery efficiency. As a result, the cycling life of a battery having OH-TEMPO as active species in the catholyte and containing propylene carbonate-based anolyte was evaluated over 300 cycles, achieving 85% capacity retention. These results demonstrated the huge versatility and countless possibilities of this new membrane-free battery concept.

Pioneering Use of Ionic Liquid-Based Aqueous Biphasic Systems as Membrane-Free Batteries.

Aqueous biphasic systems (ABS) formed by water, ionic liquids (ILs), and salts, in which the two phases are water rich, are demonstrated here to act as potential membrane-free batteries. This concept is feasible due to the selective enrichment of redox organic molecules in each aqueous phase of ABS, which spontaneously form two liquid-phases above given concentrations of salt and IL. Therefore, the required separation of electrolytes in the battery is not driven by an expensive membrane that hampers mass transfer, but instead, by the intrinsic immiscibility of the two liquid phases. Moreover, the crosscontamination typically occurring through the ineffective membranes is determined by the partition coefficients of the active molecules between the two phases. The phase diagrams of a series of IL-based ABS are characterized, the partition coefficients of several redox organic molecules are determined, and the electrochemistry of these redox-active immiscible phases is evaluated, allowing appraisal of the battery performance. Several redox ABS that may be used in total aqueous membrane-free batteries with theoretical battery voltages as high as 1.6 V are identified. The viability of a membrane-free battery composed of an IL-based ABS containing methyl viologen and 2,2,6,6-tetramethyl-1-piperidinyloxy as active species is demonstrated.

Metagenome Sequences of Sediment from a Recovering Industrialized Appalachian River in West Virginia.

We sequenced two metagenomes from upper sediment layers (0 to 5 and 6 to 10 cm) from the Kanawha River, West Virginia. The watershed includes inputs from the forested Appalachian Mountains, surface coal mining, municipal residues, and extensive chemical manufacturing. The dominant bacterial phyla were Proteobacteria, Bacteriodetes, Firmicutes, Actinobacteria, and Chloroflexi Xenobiotic degradation pathways were present.

Metagenome Sequences of a Thermophilic Anaerobic Digester Adapted to a Low C/N Ratio, High-Ammonia Feedstock (Poultry Litter).

We sequenced the metagenome of a pilot-scale thermophilic digester with long-term, stable performance on poultry litter feedstock which has a very low C/N ratio, a high ammonia level, and high lignocellulose content. Firmicutes were the dominant phylum (68.9%). Other abundant phyla included Bacteroidetes, Euryarchaeota, and Thermotogae This microbiome represents a hydrogenotrophic methanogenic community with high diversity.