Single Functional Group Research Articles

High‐Performance Aqueous Zinc Batteries Based on Organic/Organic Cathodes Integrating Multiredox Centers

AbstractOrganic cathode materials with redox‐active sites and flexible structure are promising for developing aqueous zinc ion batteries with high capacity and large output power. However, the energy storage of most organic hosts relies on the coordination/incoordination reaction between Zn2+/H+ and a single functional group, which result in inferior capacity, low discharge platform, and structural instability. Here, the lead is taken in in situ electrodepositing stable poly(1,5‐naphthalenediamine, 1,5‐NAPD) as interlayer and excellent conductive poly(para‐aminophenol, pAP) skin onto nanoporous carbon in sequence for the structural optimization of organic/organic cathodes, designated as C@multi‐layer polymer. In situ analyses, electrochemical measurements, and theoretical calculation prove that both CO and CN active groups can act as a strong electron donor as well as Zn2+ host during the discharging process. Benefiting from the synergistic effect of the double organic layers, C@multi‐layer polymer delivers high capacity, long lifespan, and excellent capacity reservation even at large discharge current and commercial mass loading (>10 mg cm−2). Introducing multiredox centers into one organic composites will provide new insights into designing advanced Zn–organic batteries.

DFT study on the effect of functional groups of carbonaceous surface on ammonium adsorption from water

Density functional theory (DFT) was used to study the adsorption of ammonium ion on carbon materials. The effects of single and multiple adjacent functional groups of carbon structures on ammonium ion adsorption were emphasized. The electrostatic potential, adsorption energy, charge transfer, molecular orbital, and dipole moment of different configurations were analyzed. Results showed that the carbonyl group was more likely to adsorb ammonium ion than lactone, carboxyl, and hydroxyl. When the carbon material contained multiple adjacent functional groups at the same time, the adsorption of ammonium ion can be promoted or inhibited due to the interaction among functional groups. The effect of functional groups on the adsorption of π bond in carbon materials was related to the electronegativity of functional groups, i.e., greater electronegativity led to smaller adsorption energy of π bond. Carbon material itself is nonpolar and hydrophobic, so adding oxygen-containing functional groups can increase the dipole moment of carbon material molecules, thereby enhancing its polarity and adsorption capacity.

Controlling the Reactivity of a Metal-Hydroxo Adduct with a Hydrogen Bond.

The enzymes manganese lipoxygenase (MnLOX) and manganese superoxide dismutase (MnSOD) utilize mononuclear Mn centers to effect their catalytic reactions. In the oxidized MnIII state, the active site of each enzyme contains a hydroxo ligand, and X-ray crystal structures imply a hydrogen bond between this hydroxo ligand and a cis carboxylate ligand. While hydrogen bonding is a common feature of enzyme active sites, the importance of this particular hydroxo-carboxylate interaction is relatively unexplored. In this present study, we examined a pair of MnIII-hydroxo complexes that differ by a single functional group. One of these complexes, [MnIII(OH)(PaPy2N)]+, contains a naphthyridinyl moiety capable of forming an intramolecular hydrogen bond with the hydroxo ligand. The second complex, [MnIII(OH)(PaPy2Q)]+, contains a quinolinyl moiety that does not permit any intramolecular hydrogen bonding. Spectroscopic characterization of these complexes supports a common structure, but with perturbations to [MnIII(OH)(PaPy2N)]+, consistent with a hydrogen bond. Kinetic studies using a variety of substrates with activated O-H bonds, revealed that [MnIII(OH)(PaPy2N)]+ is far more reactive than [MnIII(OH)(PaPy2Q)]+, with rate enhancements of 15-100-fold. A detailed analysis of the thermodynamic contributions to these reactions using DFT computations reveals that the former complex is significantly more basic. This increased basicity counteracts the more negative reduction potential of this complex, leading to a stronger O-H BDFE in the [MnII(OH2)(PaPy2N)]+ product. Thus, the differences in reactivity between [MnIII(OH)(PaPy2Q)]+ and [MnIII(OH)(PaPy2N)]+ can be understood on the basis of thermodynamic considerations, which are strongly influenced by the ability of the latter complex to form an intramolecular hydrogen bond.

Predicting gas–particle partitioning coefficients of atmospheric molecules with machine learning

Abstract. The formation, properties, and lifetime of secondary organic aerosols in the atmosphere are largely determined by gas–particle partitioning coefficients of the participating organic vapours. Since these coefficients are often difficult to measure and to compute, we developed a machine learning model to predict them given molecular structure as input. Our data-driven approach is based on the dataset by Wang et al. (2017), who computed the partitioning coefficients and saturation vapour pressures of 3414 atmospheric oxidation products from the Master Chemical Mechanism using the COSMOtherm programme. We trained a kernel ridge regression (KRR) machine learning model on the saturation vapour pressure (Psat) and on two equilibrium partitioning coefficients: between a water-insoluble organic matter phase and the gas phase (KWIOM/G) and between an infinitely dilute solution with pure water and the gas phase (KW/G). For the input representation of the atomic structure of each organic molecule to the machine, we tested different descriptors. We find that the many-body tensor representation (MBTR) works best for our application, but the topological fingerprint (TopFP) approach is almost as good and computationally cheaper to evaluate. Our best machine learning model (KRR with a Gaussian kernel + MBTR) predicts Psat and KWIOM/G to within 0.3 logarithmic units and KW/G to within 0.4 logarithmic units of the original COSMOtherm calculations. This is equal to or better than the typical accuracy of COSMOtherm predictions compared to experimental data (where available). We then applied our machine learning model to a dataset of 35 383 molecules that we generated based on a carbon-10 backbone functionalized with zero to six carboxyl, carbonyl, or hydroxyl groups to evaluate its performance for polyfunctional compounds with potentially low Psat. The resulting saturation vapour pressure and partitioning coefficient distributions were physico-chemically reasonable, for example, in terms of the average effects of the addition of single functional groups. The volatility predictions for the most highly oxidized compounds were in qualitative agreement with experimentally inferred volatilities of, for example, α-pinene oxidation products with as yet unknown structures but similar elemental compositions.

Palladium-Catalyzed γ,γ'-Diarylation of Free Alkenyl Amines.

The direct difunctionalization of alkenes is an effective way to construct multiple C-C bonds in one-pot using a single functional group. The regioselective dicarbofunctionalization of alkenes is therefore an important area of research to rapidly obtain complex organic molecules. Herein, we report a palladium-catalyzed γ,γ'-diarylation of free alkenyl amines through interrupted chain walking for the synthesis of Z-selective alkenyl amines. Notably, while 1,3-dicarbofunctionalization of allyl groups is well precedented, the present disclosure allows 1,3-dicarbofunctionalization of highly substituted allylamines to give highly Z-selective trisubsubstituted olefin products. This cascade reaction operates via an unprotected amine-directed Mizoroki-Heck (MH) pathway featuring a β-hydride elimination to selectively chain walk to furnish a new terminal olefin which then generates the cis-selective alkenyl amines around the sterically crowded allyl moiety. This operationally simple protocol is applicable to a variety of cyclic, branched, and linear secondary and tertiary alkenylamines, and has a broad substrate scope with regard to the arene coupling partner as well. Mechanistic studies have been performed to help elucidate the mechanism, including the presence of a likely unproductive side C-H activation pathway.

Niche adaptation promoted the evolutionary diversification of tiny ocean predators

Unicellular eukaryotic predators play a crucial role in the functioning of the ocean ecosystem by recycling nutrients and energy that are channeled to upper trophic levels. Traditionally, these evolutionarily diverse organisms have been combined into a single functional group (heterotrophic flagellates), overlooking their organismal differences. Here, we investigated four evolutionarily related species belonging to one cosmopolitan group of uncultured marine picoeukaryotic predators: marine stramenopiles (MAST)-4 (species A, B, C, and E). Co-occurrence and distribution analyses in the global surface ocean indicated contrasting patterns in MAST-4A and C, suggesting adaptation to different temperatures. We then investigated whether these spatial distribution patterns were mirrored by MAST-4 genomic content using single-cell genomics. Analyses of 69 single cells recovered 66 to 83% of the MAST-4A/B/C/E genomes, which displayed substantial interspecies divergence. MAST-4 genomes were similar in terms of broad gene functional categories, but they differed in enzymes of ecological relevance, such as glycoside hydrolases (GHs), which are part of the food degradation machinery in MAST-4. Interestingly, MAST-4 species featuring a similar GH composition (A and C) coexcluded each other in the surface global ocean, while species with a different set of GHs (B and C) appeared to be able to coexist, suggesting further niche diversification associated with prey digestion. We propose that differential niche adaptation to temperature and prey type has promoted adaptive evolutionary diversification in MAST-4. We show that minute ocean predators from the same phylogenetic group may have different biogeography and genomic content, which needs to be accounted for to better comprehend marine food webs.

A chemical and bio‐herbicide mixture increased exotic invaders, both targeted and non‐targeted, across a diversely invaded landscape after fire

AbstractQuestionsInvasive‐plant treatments often target a single or few species, but many landscapes are diversely invaded. Exotic annual grasses (EAGs) increase wildfires and degrade native perennial plant communities in cold‐desert rangelands, and herbicides are thus sprayed to inhibit EAG germination and establishment. We asked how EAG target and non‐target species responded to an herbicide mixture sprayed over a large, topographically diverse landscape after wildfire. We focused on how whole‐community and natural EAG‐pathogen treatment responses varied over years and physical properties of sites.LocationSagebrush steppe of southwest Idaho, USA.MethodsWe monitored plant cover and diversity in 41 pairs of plots located inside or outside areas (486 ha total) treated with a combined aerial broadcast spray of pre‐emergent herbicide (imazapic) and weed‐suppressive bacteria (Pseudomonas fluorescens, “MB906”) to target EAGs after wildfires.ResultsEAG cover and exotic species richness were initially less in treated plots but increased to levels similar to or greater than those of untreated plots by the third post‐treatment year. The EAG pathogen Ustilago bullata was not directly affected by the treatment. The treatment increased exotic perennial forb cover in all plots and exotic annual forb cover in cooler/wetter plots but reduced exotic annual forb cover in warmer/drier plots. Cover of the invasive biennial grass Poa bulbosa decreased more across study years in untreated than treated plots. Among natives, the treatment reduced perennial grass cover and annual forb presence but led to marginal increases in perennial forb cover and, on soils with less gravel, increased shrub presence.ConclusionsA treatment targeting a single plant functional group did not achieve lasting success in these diversely invaded communities. Spraying alone did not release native perennials sufficiently to counteract the simultaneous release of secondary invaders and the return of target invaders. Planting or seeding may also be needed to achieve management goals.

One Atom Makes All the Difference: Getting a Foot in the Door between SOS1 and KRAS.

KRAS, the most common oncogenic driver in human cancers, is controlled and signals primarily through protein-protein interactions (PPIs). The interaction between KRAS and SOS1, crucial for the activation of KRAS, is a typical, challenging PPI with a large contact surface area and high affinity. Here, we report that the addition of only one atom placed between Y884SOS1 and A73KRAS is sufficient to convert SOS1 activators into SOS1 inhibitors. We also disclose the discovery of BI-3406. Combination with the upstream EGFR inhibitor afatinib shows in vivo efficacy against KRASG13D mutant colorectal tumor cells, demonstrating the utility of BI-3406 to probe SOS1 biology. These findings challenge the dogma that large molecules are required to disrupt challenging PPIs. Instead, a "foot in the door" approach, whereby single atoms or small functional groups placed between key PPI interactions, can lead to potent inhibitors even for challenging PPIs such as SOS1-KRAS.

Anion Exchange Ionomers: Impact of Chemistry on Thin‐Film Properties

AbstractIonomer thin‐films (i.e., 20–100 nm) on supports serve as model systems to understand ionomer‐catalyst interfacial behavior as well as the confinement‐driven deviation in properties from bulk membranes. While ionomer thin‐films have been examined for proton exchange ionomers, the thin‐film properties of anion exchange ionomers (AEIs) remain largely unexplored. More importantly, delineating the convoluted impact of chemistry and confinement on thin‐film morphology and hydration is of interest to advancing the field on functional ionic interfaces. In this work, these aspects are studied by using AEIs of different backbones (perfluorinated, aliphatic, and aromatic) and side chains (various lengths, and single versus dual functional groups). Quartz‐crystal microbalance and spectroscopic ellipsometry are used to analyze density and coupled with calculated free volume fraction of thin‐films to provide insights on their gas transport properties. AEI side‐chain's chemical character plays a key role in how confinement modulates hydration (in thin‐film versus bulk). The results elucidate the effects of backbone, side‐chain chemistry versus anion/cation type in the confinement‐driven changes in thin‐film morphology and swelling. This study also provides new insights for tuning AEI transport functionalities at interfaces via chemistry, which can benefit the design and development of electrode‐ionomers for alkaline membrane‐based energy systems.

Soil biological response to multi-species cover crops in the Northern Great Plains

Farmers in semi-arid regions are experimenting with cover crop mixtures as partial summer fallow replacement, with the goal of increasing soil biological activity. We compared extracellular enzyme activity, microbial biomass, potentially mineralizable nitrogen (PMN) and mycorrhizal colonization levels after growing cover crops comprised of one or four functional groups. We asked whether cover crops can alter those soil processes and components relative to fallow during the cash crop growing season, and whether a cover crop mixture (CCM) will have a greater impact than a single-species legume green manure (LGM) after one and two rotations with wheat. Cover crops were planted at two sites in Montana April 2012 and May 2014, and at two additional sites in May 2013, and April 2015, terminated at each site approximately 60 days after seeding. Wheat was the cash crop for the following growing season. Cover crop treatments included a fallow control, a sole pea LGM, and a FULL mix consisting of eight species, with two species of each of four functional groups. Four additional treatments of single functional groups were compared following the second rotation of cover crops. The geometric mean of soil enzyme activity increased after cover crops relative to fallow (1.1–1.3 fold) at two sites after the first rotation, and by 1.1–1.4 fold after the second rotation at three sites. At the fourth site, the geometric mean of the FULL mix was greater than LGM or fallow by 1.4 and 1.5 fold. The response of individual enzymes was less consistent. Microbial biomass and PMN increased after LGM and/or FULL at three of eight site-years, by 1.2–1.7 for microbial biomass and 1.6–2.1 for PMN. Mycorrhizal colonization of wheat increased in at least one cover crop treatment relative to fallow at four of six site-years, and decreased in cover crops relative to fallow at one site. There were no differences in soil biological traits measured among single-functional-group treatments. Soil biological parameters were correlated with cover crop biomass in 7 of 16 comparisons at two sites after one rotation. After two rotations, 5 of 8 soil parameters were correlated with cover crop biomass at one site, with no correlations for the remaining sites. Precipitation declined 30–50 % from the first rotations at those three sites. Positive effects of cover crops on soil biological parameters in semi-arid systems may be measurable only when environmental conditions do not limit growth.

Thermo- and Photoresponsive Behaviors of Dual-Stimuli-Responsive Organogels Consisting of Homopolymers of Coumarin-Containing Methacrylate.

Coumarin-containing vinyl homopolymers, such as poly(7-methacryloyloxycoumarin) (P1a) and poly(7-(2′-methacryloyloxyethoxy)coumarin) (P1b), show a lower critical solution temperature (LCST) in chloroform, which can be controlled by the [2 + 2] photochemical cycloaddition of the coumarin moiety, and they are recognized as monofunctional dual-stimuli-responsive polymers. A single functional group of monofunctional dual-stimuli-responsive polymers responds to dual stimuli and can be introduced more uniformly and densely than those of dual-functional dual-stimuli-responsive polymers. In this study, considering a wide range of applications, organogels consisting of P1a and P1b, i.e., P1a-gel and P1b-gel, respectively, were synthesized, and their thermo- and photoresponsive behaviors in chloroform were investigated in detail. P1a-gel and P1b-gel in a swollen state (transparent) exhibited phase separation (turbid) through a temperature jump and reached a shrunken state (transparent), i.e., an equilibrium state, over time. Moreover, the equilibrium degree of swelling decreased non-linearly with increasing temperature. Furthermore, different thermoresponsive sites were photopatterned on the organogel through the photodimerization of the coumarin unit. The organogels consisting of homopolymers of coumarin-containing methacrylate exhibited unique thermo- and photoresponsivities and behaved as monofunctional dual-stimuli-responsive organogels.

Coping with dynamical reaction system topologies using deterministic P modules: a case study of photosynthesis

The topology of chemical reaction networks is commonly treated as a static structure. This might be sufficient if substrate concentrations and kinetic parameter values exclusively determine the behaviour of all considered reactions. In contrast, numerous phenomena observed in life sciences imply a different nature by dynamical composition of reaction schemes. Single reactions or functional groups of reactions (modules) become activated or deactivated by external signals such as light intensity while the system is in operation. In other scenarios, reactions emerge or disappear while modules can connect to each other or disconnect due to presence or absence of corresponding trigger signals. We capture dynamical reaction network structures by an extended version of deterministic P modules with evaluation of trigger signals which facilitates detailed in-silico simulation studies and hence an easier understanding and prediction of complex biological systems. A case study dedicated to photosynthesis in plants demonstrates its usefulness beyond pure employment of ordinary differential equations by consideration of events, non-differentiable external trigger signals, and thresholds which collaterally modify the underlying reaction scheme.

Study of surface heterogeneity and nitrogen functionalizing of biochars: Molecular modeling approach

The functionality of biochar surfaces depends on the nature of the feedstock, pyrolysis temperature, and residence time. In this study, molecular modeling was used to determine the types of functionalization that could enhance adsorption and to pre-screen the target adsorbate for the sake of minimizing experimental time. The impact of a single functional group and interaction between them (including nitrile, methyl, ether, furan, carboxyl, hydroxyl, amine, and amide) on the adsorption of target adsorbate onto biochar was investigated. Among biochars inherent functional groups simulated, the lowest energy of adsorption (highest adsorption) occurred with carboxyl and hydroxyl for CO2 adsorption due to hydrogen bonding. The simulations showed adding amine/amide functional groups to the biochar surface enhanced CO2 adsorption, because of stronger bonding. The simulation results were compared against experimental results and the thermodynamic properties were satisfactorily matched. The overall heat of adsorption of H2S was lower than CO2, but the average Gibbs free energy was approximately the same, indicating CO2 could replace H2S in initial screening adsorption experiments for this type of biochar, reducing costs, risk and toxicity concerns of using H2S. This is an example of potentially how the models can be used to better design experiments.

Reversible Functionalization of Clickable Polyacrylamide Gels with Protein and Graft Copolymers.

Modular strategies to fabricate gels with tailorable chemical functionalities are relevant to applications spanning from biomedicine to analytical chemistry. Here, the properties of clickable poly(acrylamide-co-propargyl acrylate) (pAPA) hydrogels are modified via sequential in-gel copper-catalyzed azide-alkyne cycloaddition (CuAAC) reactions. Under optimized conditions, each in-gel CuAAC reaction proceeds with rate constants of ~0.003 s-1, ensuring uniform modifications for gels < 200 μm thick. Using the modular functionalization approach and a cleavable disulfide linker, pAPA gels were modified with benzophenone and acrylate groups. Benzophenone groups allow gel functionalization with unmodified proteins using photoactivation. Acrylate groups enabled copolymer grafting onto the gels. To release the functionalized unit, pAPA gels were treated with disulfide reducing agents, which triggered ~50 % release of immobilized protein and grafted copolymers. The molecular mass of grafted copolymers (~6.2 kDa) was estimated by monitoring the release process, expanding the tools available to characterize copolymers grafted onto hydrogels. Investigation of the efficiency of in-gel CuAAC reactions revealed limitations of the sequential modification approach, as well as guidelines to convert a pAPA gel with a single functional group into a gel with three distinct functionalities. Taken together, we see this modular framework to engineer multifunctional hydrogels as benefiting applications of hydrogels in drug delivery, tissue engineering, and separation science.

Identification of the subtype-selective Sirt5 inhibitor balsalazide through systematic SAR analysis and rationalization via theoretical investigations.

We report here an extensive structure-activity relationship study of balsalazide, which was previously identified in a high-throughput screening as an inhibitor of Sirt5. To get a closer understanding why this compound is able to inhibit Sirt5, we initially performed docking experiments comparing the binding mode of a succinylated peptide as the natural substrate and balsalazide with Sirt5 in the presence of NAD+. Based on the evidence gathered here, we designed and synthesized 13 analogues of balsalazide, in which single functional groups were either deleted or slightly altered to investigate which of them are mandatory for high inhibitory activity. Our study confirms that balsalazide with all its given functional groups is an inhibitor of Sirt5 in the low micromolar concentration range and structural modifications presented in this study did not increase potency. While changes on the N-aroyl-β-alanine side chain eliminated potency, the introduction of a truncated salicylic acid part minimally altered potency. Calculations of the associated reaction paths showed that the inhibition potency is very likely dominated by the stability of the inhibitor-enzyme complex and not the type of inhibition (covalent vs. non-covalent). Further in-vitro characterization in a trypsin coupled assay determined that the tested inhibitors showed no competition towards NAD+ or the synthetic substrate analogue ZKsA. In addition, investigations for subtype selectivity revealed that balsalazide is a subtype-selective Sirt5 inhibitor, and our initial SAR and docking studies pave the way for further optimization.

Can mandible morphology help predict feeding habits in Antarctic amphipods?

AbstractIn Antarctica, amphipods form a highly diverse group, occupy many different ecological niches and hold an important place in food webs. Here, we aimed to test whether differences in Antarctic amphipod feeding habits were reflected in their mandible morphology, and if mouthpart specialization could be used to describe amphipod trophic ecology. To do so, we compared mandible morphology in nine species spanning seven families and five functional groups (grazers, suspension feeders, generalist predators, specialist predators and scavengers). Mandible morphology adequately depicted some aspects of amphipod trophic ecology, such as the trophic level at which animals feed or their degree of dietary specialization. On the other hand, links between mandible morphology and amphipod diet were seldom unambiguous or straightforward. Similar adaptations were found in distinct functional groups. Conversely, mandible morphology could vary within a single functional group, and phylogenetic effects sometimes complicated the interpretation of form-function relationships. Overall, mandible morphology on its own was generally not sufficient to precisely predict amphipod feeding strategies. However, when combined with other methods (e.g. gut contents, trophic markers), it constitutes a valuable source of information for integrative studies of amphipod ecological diversity in the Southern Ocean.

FTIR analysis of chemical changes in wood induced by steaming and longitudinal compression

Pleating is an optimal way to increase bendability of wood used in diverse industrial applications. It results in the excessive buckling of cell walls and modifications of constitutive polymers. However, thoughtful understanding of the physical–chemical mechanisms of that modification process is very limited. The main purpose of the present study was to identify changes in functional groups of wood polymers induced by longitudinal compression. Four types of wood samples prepared from beech and sessile oak (untreated, steamed, longitudinally compressed and fixated for 1 min as well as longitudinally compressed and fixated for 18 h) were assessed by infrared spectroscopy. The spectra interpretation revealed that changes can be observed in hydroxyl as well as in carbon–oxygen single and carbon-hydrogen functional groups of polysaccharides and lignin. Beech wood seems to be more susceptible to investigated modification processes as compared to oak. Detailed interpretation of infrared spectra allows identification of changes in the hygroscopicity of wood as well as alterations in the linkage between structural elements in the polymer matrix of wood induced by the applied treatments.Graphic

Modelling the nutritional strategies in mixotrophic nanoflagellates

Mixotrophic nanoflagellates (MNF) play a key role in the carbon flux within aquatic ecosystems. They contribute significantly to primary production while, at the same time, they are important consumers of bacteria. MNF comprise a diverse assemblage with a whole range of photosynthetic and feeding potential and with various metabolic responses to environmental drivers, such as light, nutrients and prey availability. However, in most cases MNF are modelled as a single functional group with no reference to the distinct nutritional strategies and constraints of the different types of MNF. Here we develop a mathematical framework for the distinct functional responses of four types of MNF. Our approach is based on the Dynamic Energy Budget (DEB) theory and the concept of Synthesing Unit (SU), which is used to merge phototrophic and phagotrophic nutrition into mixotrophic growth. The resulting models describe explicitly the functional diversity of the MNF group taking into account the dynamic interaction of phototrophy and phagotrophy within the four types of MNF. Our results are in agreement with theoretical expectations and a wide range of experimental observations for the different types of MNF. Our simulations suggest that the growth dynamics of the four types of MNF are affected differently by the availability of resources. Moreover, using our models to compare the rates of organic carbon production and prey consumption by the various MNF types, we show that their net ecosystem role, as producers or consumers, depends on the mixotrophic strategy and it can vary as a function of the prevailing environmental conditions. Overall, our study highlights the importance of mechanistically modelling the distinct metabolic responses of the different types of MNF to environmental drivers in order to better understand their role in the carbon cycle in anticipation of global environmental changes.

Wood-Derived Carbon with Selectively Introduced C═O Groups toward Stable and High Capacity Anodes for Sodium Storage.

Biomass-derived carbon is a promising sustainable anode material for sodium-ion batteries (SIBs). Although the electrochemical performance can be improved by introducing functional groups, the selective introduction of single functional groups into biomass carbon remains difficult. Here, we overcome this challenge by developing a wood-derived carbon with selectively introduced C═O groups by combining tetramethoxysilane (TMOS) with wood cellulose pulps. The integration of TMOS introduces abundant C═O groups into the carbon during the polycondensation and pyrolysis process. The C═O groups play a dominant role in anode surface-controlled processes, and this leads to improvements in pseudo-capacity and fast electrode process kinetics. Besides, the introduction of C═O groups generates oxygen functional active sites that promote Na+ adsorption and creates a sufficiently largegraphene interlayer distance. The as-obtained carbon shows a high capacity of 330 mAh g-1 at 40 mA g-1 and excellent cycling stability. Moreover, our strategy is simple and uses wood cellulose pulps as precursors. It therefore enables low-cost and large-scale synthesis of carbon anode materials for SIBs.

A Bi-functional Second Coordination Sphere for Electrocatalytic CO2 Reduction: The Concerted Improvement by a Local Proton Source and Local Coulombic Interactions

A homogeneous rhenium(I) electrocatalyst possessing hydroxy and ammonio groups in the second coordination sphere is reported for the reduction of carbon dioxide (CO2) to carbon monoxide, wherein the former and latter groups induce a high local concentration of protons and local coulombic interactions with a metallocarboxylate reaction intermediate, respectively. In a comparison with precedent catalysts possessing single functional groups in the spheres, we found that the catalyst exhibits a concerted improvement over these single functional groups in the efficiencies of catalysis, based on experimental standard electrode potentials for the reduction in aqueous N,N-dimethylformamide or acetonitrile solutions and the equilibrium potentials depending on the catalytic systems.