The Effect of the SEI Layer Mechanical Deformation on the Passivity of a Si Anode in Organic Carbonate Electrolytes.

The solid electrolyte interphase (SEI) on a Si negative electrode in carbonate-based organic electrolytes shows intrinsically poor passivating behavior, giving rise to unsatisfactory calendar life of Li-ion batteries. Moreover, mechanical strains induced in the SEI due to large volume changes of Si during charge-discharge cycling could contribute to its mechanical instability and poor passivating behavior. This study elucidates the influence that static mechanical deformation of the SEI has on the rate of unwanted parasitic reactions at the Si/electrolyte interface as a function of electrode potential. The experimental approach involves the utilization of Si thin-film electrodes on substrates with disparate elastic moduli, which either permit or suppress the SEI deformation in response to Si volume changes upon charging-discharging. We find that static mechanical stretching and deformation of the SEI results in an increased parasitic electrolyte reduction current on Si. Furthermore, attenuated total reflection and near-field Fourier-transform infrared nanospectroscopy reveal that the static mechanical stretching and deformation of the SEI fosters a selective transport of linear carbonate solvent through, and nanoconfinement within, the SEI. These, in turn, promote selective solvent reduction and continuous electrolyte decomposition on Si electrodes, reducing the calendar life of Si anode-based Li-ion batteries. Finally, possible correlations between the structure and chemical composition of the SEI layer and its mechanical and chemical resilience under prolonged mechanical deformation are discussed in detail.

Recent Applications of Langmuir-Blodgett Technique in Battery Research.

The Langmuir-Blodgett (LB) technique, in which monolayers are commonly transferred from a liquid/gas interface to a solid surface, allows convenient fabrication of highly ordered thin films with molecular-level precision. This method is widely applicable to substances ranging from organic molecules to nanomaterials. Therefore, LB methods have provided a critical toolbox for researchers to engineer nanoarchitectures. The LB fabrication process is also compatible with numerous substrate materials over large areas, which is advantageous for practical application. Despite its wide applicability, the LB strategy has not been extensively employed in battery studies. The versatility of LB film, along with the accumulated knowledge associated with this technique, makes it a promising platform for promoting battery chemistry evolution. This Review summarizes recent advances of LB methods for high-performance battery development, including preparation of electrode materials, fabrication of functional layers, and battery diagnosis and thus illustrates the high utility of LB approaches in battery research.

In Situ Measurement of the Plane-Strain Modulus of the Solid Electrolyte Interphase on Lithium-Metal Anodes in Ionic Liquid Electrolytes.

We present an experimental approach for in situ measurement of elastic modulus of the solid electrolyte interphase (SEI), which is formed from reactions between a lithium thin-film [on a polydimethylsiloxane (PDMS) substrate] and a room-temperature ionic liquid (RTIL) electrolyte. The SEI forms under a state of compressive stress, which causes buckling of the sample surface. In situ atomic force microscopy is used to measure the dominant wavelength of the wrinkled surface topography. A mechanics analysis of strain-induced elastic buckling instability of a stiff thin film on a soft substrate is used to determine the plane strain modulus of the SEI from the measured wavelength. The measurements are performed for three RTIL electrolytes: 1-butyl 1-methylpiperidinium bis(trifluoromethylsulfonyl)imide (P14 TFSI) without any lithium salt, 1.0 M lithium bis(trifluoromethylsulfonyl)imide (Li TFSI) in P14 TFSI, and 1.0 M lithium bis(fluorosulfonyl)imide (Li FSI) in P14 TFSI to investigate the influence of lithium salts on the plane strain modulus of the SEI. The measurements yield plane-strain moduli of approximately 1.3 GPa for no-salt P14 TFSI and approximately 1.6 GPa for 1.0 M Li TFSI in P14 TFSI and 1.0 M Li FSI in P14 TFSI. The experimental technique presented here eliminates some of the uncertainties associated with traditional SEI mechanical characterization approaches and offers a platform to engineer an SEI with desired mechanical properties by approaches that include altering the electrolyte composition.

The protein phosphatase 2C clade A protein OsPP2C51 positively regulates seed germination by directly inactivating OsbZIP10.

Protein phosphatase 2C clade A members are major signaling components in the ABA-dependent signaling cascade that regulates seed germination. To elucidate the role of PP2CA genes in germination of rice seed, we selected OsPP2C51, which shows highly specific expression in the embryo compared with other protein phosphatases based on microarray data. GUS histochemical assay confirmed that OsPP2C51 is expressed in the seed embryo and that this expression pattern is unique compared with those of other OsPP2CA genes. Data obtained from germination assays and alpha-amylase assays of OsPP2C51 knockout and overexpression lines suggest that OsPP2C51 positively regulates seed germination in rice. The expression of alpha-amylase synthesizing genes was high in OsPP2C51 overexpressing plants, suggesting that elevated levels of OsPP2C51 might enhance gene expression related to higher rates of seed germination. Analysis of protein interactions between ABA signaling components showed that OsPP2C51 interacts with OsPYL/RCAR5 in an ABA-dependent manner. Furthermore, interactions were observed between OsPP2C51 and SAPK2, and between OsPP2C51 and OsbZIP10 and we found out that OsPP2C51 can dephosphorylates OsbZIP10. These findings suggest the existence of a new branch in ABA signaling pathway consisting of OsPYL/RCAR-OsPP2C-bZIP apart from the previously reported OsPYL/RCAR-OsPP2C-SAPK-bZIP. Overall, our result suggests that OsPP2C51 is a positive regulator of seed germination by directly suppressing active phosphorylated OsbZIP10.

Functional characterization and reconstitution of ABA signaling components using transient gene expression in rice protoplasts.

The core components of ABA-dependent gene expression signaling have been identified in Arabidopsis and rice. This signaling pathway consists of four major components; group A OsbZIPs, SAPKs, subclass A OsPP2Cs and OsPYL/RCARs in rice. These might be able to make thousands of combinations through interaction networks resulting in diverse signaling responses. We tried to characterize those gene functions using transient gene expression for rice protoplasts (TGERP) because it is instantaneous and convenient system. Firstly, in order to monitor the ABA signaling output, we developed reporter system named pRab16A-fLUC which consists of Rab16A promoter of rice and luciferase gene. It responses more rapidly and sensitively to ABA than pABRC3-fLUC that consists of ABRC3 of HVA1 promoter in TGERP. We screened the reporter responses for over-expression of each signaling components from group A OsbZIPs to OsPYL/RCARs with or without ABA in TGERP. OsbZIP46 induced reporter most strongly among OsbZIPs tested in the presence of ABA. SAPKs could activate the OsbZIP46 even in the ABA independence. Subclass A OsPP2C6 and -8 almost completely inhibited the OsbZIP46 activity in the different degree through the SAPK9. Lastly, OsPYL/RCAR2 and -5 rescued the OsbZIP46 activity in the presence of SAPK9 and OsPP2C6 dependent on ABA concentration and expression level. By using TGERP, we could characterize successfully the effects of ABA dependent gene expression signaling components in rice. In conclusion, TGERP represents very useful technology to study systemic functional genomics in rice or other monocots.

Double emulsion templated monodisperse phospholipid vesicles.

We present a novel approach for fabricating monodisperse phospholipid vesicles with high encapsulation efficiency using controlled double emulsions as templates. Glass-capillary microfluidics is used to generate monodisperse double emulsion templates. We show that the high uniformity in size and shape of the templates are maintained in the final phospholipid vesicles after a solvent removal step. Our simple and versatile technique is applicable to a wide range of phospholipids.

A rice dehydration-inducible SNF1-related protein kinase 2 phosphorylates an abscisic acid responsive element-binding factor and associates with ABA signaling.

By a differential cDNA screening technique, we have isolated a dehydration-inducible gene (designated OSRK1) that encodes a 41.8 kD protein kinase of SnRK2 family from Oryza sativa. The OSRK1 transcript level was undetectable in vegetative tissues, but significantly increased by hyperosmotic stress and Abscisic acid (ABA). To determine its biochemical properties, we expressed and isolated OSRK1 and its mutants as glutathione S-transferase fusion proteins in Escherichia coli. In vitro kinase assay showed that OSRK1 can phosphorylate itself and generic substrates as well. Interestingly, OSRK1 showed strong substrate preference for rice bZIP transcription factors and uncommon cofactor requirement for Mn(2+) over Mg(2+). By deletion of C-terminus 73 amino acids or mutations of Ser-158 and Thr-159 to aspartic acids (Asp) in the activation loop, the activity of OSRK1 was dramatically decreased. OSRK1 can transphosphorylate the inactive deletion protein. A rice family of abscisic acid-responsive element (ABRE) binding factor, OREB1 was phosphorylated in vitro by OSRK1 at multiple sites of different functional domains. MALDI-TOF analysis identified a phosphorylation site at Ser44 of OREB1 and mutation of the residue greatly decreased the substrate specificity for OSRK1. The recognition motif for OSRK1, RQSS is highly similar to the consensus substrate sequence of AMPK/SNF1 kinase family. We further showed that OSRK1 interacts with OREB1 in a yeast two-hybrid system and co-localized to nuclei by transient expression analysis of GFP-fused protein in onion epidermis. Finally, ectopic expression of OSRK1 in transgenic tobacco resulted in a reduced sensitivity to ABA in seed germination and root elongation. These findings suggest that OSRK1 is associated with ABA signaling, possibly through the phosphorylation of ABF family in vivo. The interaction between SnRK2 family kinases and ABF transcription factors may constitute an important part of cross-talk mechanism in the stress signaling networks in plants.

Effects of light on the feedback control of GA-20 oxidase gene homolog in DongJinByeo seedlings.

The effects of gibberellin (GA) on the expression of GA-20 oxidase gene homolog were examined in light-grown seedlings and dark-grown seedlings of DongJinByeo. The growth rates of the stems of etiolated seedlings were faster than those of green seedlings. However, upon addition of GA to these seedlings, the stem growth rates of green seedlings were faster than those of etiolated seedlings. To understand the molecular mechanism of GA gene regulation in DongJinByeo, total RNA from DongJinByeo was hybridized with cDNA of GA-20 oxidase gene homolog. Greater accumulation of transcript of GA-20 oxidase gene homolog was observed in green seedlings than in etiolated seedlings. However, upon addition of GA, higher accumulation of the gene transcript was found in etiolated seedlings than in green seedlings, indicating that expression of the transcript of GA-20 oxidase gene homolog might be inhibited by light. These results suggest that light might regulate feedback control of the transcript of GA-20 oxidase gene homolog in DongJinByeo.