SSR1 is involved in maintaining the function of mitochondria electron transport chain and iron homeostasis upon proline treatment in Arabidopsis.

Although increasing intracellular proline under stressed condition could help the plants survive, treating plant with high level of proline under normal condition could be inhibitory to plant growth. Among other possible mechanisms, proline-induced mitochondrial reactive oxygen species (ROS) production due to electron overflow in mitochondria electron transport chain (mETC) caused by elevated proline degradation may contribute to the proline toxicity. However, direct evidences are still elusive. Here, we reported a functional characterization of SSR1, encoding a protein localized in mitochondria matrix, in maintaining the function of mETC through analyzing the proline hypersensitive phenotype of an Arabidopsis mutant ssr1-1 with a truncated SSR1 protein. Our analysis demonstrated that upon proline treatment, there were higher mitochondrial ROS, lower ATP content, reduced activity of mETC complex I and II, and reduced iron content in ssr1-1, in comparison to the wild type. Therefore, SSR1 is involved in maintaining normal capacity of mETC in transporting electrons in a way that related to iron homeostasis. Our results also supported that normal mETC activity is required for alleviating the proline toxicity.

The F-box protein EST1 modulates salt tolerance in Arabidopsis by regulating plasma membrane Na+/H+ antiport activity.

F-box protein, one of the building blocks of the SCF complex, functions in substrate recognition of the SCF subtype of E3 ubiquitin ligase. However, the role of F-box protein in salt stress is largely elusive in plants. Here, we report the characterization of an Arabidopsis salt-tolerant mutant est1 with significantly reduced sodium content and higher Na+/H+ antiporter activity after NaCl treatment compared to the wild-type. Over-expression of EST1 resulted in increased sensitivity to salt stress, suggesting that EST1 may act as a negative regulator for salt tolerance in Arabidopsis. EST1 encodes an F-box protein, which interacts with ASK4, ASK14, and ASK18, and is likely targeted to the endoplasmic reticulum. In addition, EST1 interacts with MKK4 and negatively regulates MKK4 protein levels and the activity of the plasma membrane Na+/H+ antiporter. Our findings demonstrate the existence of an EST1-MKK4 module that mediates salt sensitivity by regulating the activity of the plasma membrane Na+/H+ antiporter. These results provide important information for engineering salt-tolerant crops.

The effect of group-substitution on the sensitization properties of alkynylrhenium(I) tricarbonyl diimine complexes adsorbed to TiO2(101) film surface: a theoretical study.

A series of dyes are designed by adding the different electron-donating (-CH3, -NH2, -OH) and electron-withdrawing groups (-Br, -Cl, -NO2) to the different ancillary ligands in the alkynylrhenium(I) tricarbonyl diimine complexes [Re(CO)3(N^N){C≡C-C6H4-CH=C(CN)(COOH)}], where N^N = 1,10-phenanthroline (phen)(1) and then investigated the sensitization properties of dyes linked to the TiO2(101) surface. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) were used to study the electronic structure, frontier molecular orbitals, and absorption spectral properties. The effect of group-substitution on sensitization properties is obvious. When the dye molecules are combined with TiO2(101) surface, not only the absorptions of some sensitizers containing -CH3 or -OH groups have red shift but also the electrons can be directly injected into the TiO2 conduction band from the dye molecules compared with the parent molecular 1. The results indicate that the designed dyes containing electron-donating groups have smaller energy gaps, better light-harvesting efficiency, sufficient driving force, and higher charge transfer efficiency as appropriate dye sensitizers. We hope it can provide valuable hints so that we can design more efficient dye sensitizers in DSSCs.

Unsaturated Ligands Seed an Order to Disorder Transition in Mixed Ligand Shells of CdSe/CdS Quantum Dots.

A phase transition within the ligand shell of core/shell quantum dots is studied in the prototypical system of colloidal CdSe/CdS quantum dots with a ligand shell composed of bound oleate (OA) and octadecylphosphonate (ODPA). The ligand shell composition is tuned using a ligand exchange procedure and quantified through proton NMR spectroscopy. Temperature-dependent photoluminescence spectroscopy reveals a signature of a phase transition within the organic ligand shell. Surprisingly, the ligand order to disorder phase transition triggers an abrupt increase in the photoluminescence quantum yield (PLQY) and full-width at half-maximum (FWHM) with increasing temperature. The temperature and width of the phase transition show a clear dependence on ligand shell composition, such that QDs with higher ODPA fractions have sharper phase transitions that occur at higher temperatures. In order to gain a molecular understanding of the changes in ligand ordering, Fourier transform infrared and vibrational sum frequency generation spectroscopies are performed. These measurements confirm that an order/disorder transition in the ligand shell tracks with the photoluminescence changes that accompany the ligand phase transition. The phase transition is simulated through a lattice model that suggests that the ligand shell is well-mixed and does not have completely segregated domains of OA and ODPA. Furthermore, we show that the unsaturated chains of OA seed disorder within the ligand shell.

IDD16 negatively regulates stomatal initiation via trans-repression of SPCH in Arabidopsis.

In Arabidopsis, the initiation and proliferation of stomatal lineage cells is controlled by SPEECHLESS (SPCH). Phosphorylation of SPCH at the post-translational level has been reported to regulate stomatal development. Here we report that IDD16 acts as a negative regulator for stomatal initiation by directly regulating SPCH transcription. In Arabidopsis, IDD16 overexpression decreased abaxial stomatal density in a dose-dependent manner. Time course analysis revealed that the initiation of stomatal precursor cells in the IDD16-OE plants was severely inhibited. Consistent with these findings, the transcription of SPCH was greatly repressed in the IDD16-OE plants. In contrast, IDD16-RNAi transgenic line resulted in enhanced stomatal density, suggesting that IDD16 is an intrinsic regulator of stomatal development. ChIP analysis indicated that IDD16 could directly bind to the SPCH promoter. Furthermore, Arabidopsis plants overexpressing IDD16 exhibited significantly increased drought tolerance and higher integrated water use efficiency (WUE) due to reduction in leaf transpiration. Collectively, our results established that IDD16 negatively regulates stomatal initiation via trans-repression of SPCH, and thus provide a practical tool for increasing plant WUE through the manipulation of IDD16 expression.

Fluoroethylene Carbonate Induces Ordered Electrolyte Interface on Silicon and Sapphire Surfaces as Revealed by Sum Frequency Generation Vibrational Spectroscopy and X-ray Reflectivity.

The cyclability of silicon anodes in lithium ion batteries (LIBs) is affected by the reduction of the electrolyte on the anode surface to produce a coating layer termed the solid electrolyte interphase (SEI). One of the key steps for a major improvement of LIBs is unraveling the SEI's structure-related diffusion properties as charge and discharge rates of LIBs are diffusion-limited. To this end, we have combined two surface sensitive techniques, sum frequency generation (SFG) vibrational spectroscopy, and X-ray reflectivity (XRR), to explore the first monolayer and to probe the first several layers of electrolyte, respectively, for solutions consisting of 1 M lithium perchlorate (LiClO4) salt dissolved in ethylene carbonate (EC) or fluoroethylene carbonate (FEC) and their mixtures (EC/FEC 7:3 and 1:1 wt %) on silicon and sapphire surfaces. Our results suggest that the addition of FEC to EC solution causes the first monolayer to rearrange itself more perpendicular to the anode surface, while subsequent layers are less affected and tend to maintain their, on average, surface-parallel arrangements. This fundamental understanding of the near-surface orientation of the electrolyte molecules can aid operational strategies for designing high-performance LIBs.

Fluoroethylene Carbonate as a Directing Agent in Amorphous Silicon Anodes: Electrolyte Interface Structure Probed by Sum Frequency Vibrational Spectroscopy and Ab Initio Molecular Dynamics.

Fluorinated compounds are added to carbonate-based electrolyte solutions in an effort to create a stable solid electrolyte interphase (SEI). The SEI mitigates detrimental electrolyte redox reactions taking place on the anode's surface upon applying a potential in order to charge (discharge) the lithium (Li) ion battery. The need for a stable SEI is dire when the anode material is silicon as silicon cracks due to its expansion and contraction upon lithiation and delithiation (charge-discharge) cycles, consequently limiting the cyclability of a silicon-based battery. Here we show the molecular structures for ethylene carbonate (EC): fluoroethylene carbonate (FEC) solutions on silicon surfaces by sum frequency generation (SFG) vibrational spectroscopy, which yields vibrational spectra of molecules at interfaces and by ab initio molecular dynamics (AIMD) simulations at open circuit potential. Our AIMD simulations and SFG spectra indicate that both EC and FEC adsorb to the amorphous silicon (a-Si) through their carbonyl group (C═O) oxygen atom with no further desorption. We show that FEC additives induce the reorientation of EC molecules to create an ordered, up-right orientation of the electrolytes on the Si surface. We suggest that this might be helpful for Li diffusion under applied potential. Furthermore, FEC becomes the dominant species at the a-Si surface as the FEC concentration increases above 20 wt %. Our finding at open circuit potential can now initiate additive design to not only act as a sacrificial compound but also to produce a better suited SEI for the use of silicon anodes in the Li-ion vehicular industry.

In Situ Potentiodynamic Analysis of the Electrolyte/Silicon Electrodes Interface Reactions--A Sum Frequency Generation Vibrational Spectroscopy Study.

The key factor in long-term use of batteries is the formation of an electrically insulating solid layer that allows lithium ion transport but stops further electrolyte redox reactions on the electrode surface, hence solid electrolyte interphase (SEI). We have studied a common electrolyte, 1.0 M LiPF6/ethylene carbonate (EC)/diethyl carbonate (DEC), reduction products on crystalline silicon (Si) electrodes in a lithium (Li) half-cell system under reaction conditions. We employed in situ sum frequency generation vibrational spectroscopy (SFG-VS) with interface sensitivity in order to probe the molecular composition of the SEI surface species under various applied potentials where electrolyte reduction is expected. We found that, with a Si(100)-hydrogen terminated wafer, a Si-ethoxy (Si-OC2H5) surface intermediate forms due to DEC decomposition. Our results suggest that the SEI surface composition varies depending on the termination of Si surface, i.e., the acidity of the Si surface. We provide the evidence of specific chemical composition of the SEI on the anode surface under reaction conditions. This supports an electrochemical electrolyte reduction mechanism in which the reduction of the DEC molecule to an ethoxy moiety plays a key role. These findings shed new light on the formation mechanism of SEI on Si anodes in particular and on SEI formation in general.

Polymer Adsorption on Graphite and CVD Graphene Surfaces Studied by Surface-Specific Vibrational Spectroscopy.

Sum-frequency vibrational spectroscopy was employed to probe polymer contaminants on chemical vapor deposition (CVD) graphene and to study alkane and polyethylene (PE) adsorption on graphite. In comparing the spectra from the two surfaces, it was found that the contaminants on CVD graphene must be long-chain alkane or PE-like molecules. PE adsorption from solution on the honeycomb surface results in a self-assembled ordered monolayer with the C-C skeleton plane perpendicular to the surface and an adsorption free energy of ∼42 kJ/mol for PE(H(CH2CH2)nH) with n ≈ 60. Such large adsorption energy is responsible for the easy contamination of CVD graphene by impurity in the polymer during standard transfer processes. Contamination can be minimized with the use of purified polymers free of PE-like impurities.

Infrared absorption of methanethiol clusters (CH3SH)n, n = 2-5, recorded with a time-of-flight mass spectrometer using IR depletion and VUV ionization.

We investigated IR spectra in the CH- and SH-stretching regions of size-selected methanethiol clusters, (CH(3)SH)(n) with n = 2-5, in a pulsed supersonic jet using infrared (IR)-vacuum ultraviolet (VUV) ionization. VUV emission at 132.50 nm served as the source of ionization in a time-of-flight mass spectrometer. Clusters were dissociated with light from a tunable IR laser before ionization. The variations in intensity of methanethiol cluster ions (CH(3)SH)(n)(+) were monitored as the IR laser light was tuned across the range 2470-3100 cm(-1). In the SH-stretching region, the spectrum of (CH(3)SH)(2) shows a weak band near 2601 cm(-1), red-shifted only 7 cm(-1) from that of the monomer. In contrast, all spectra of (CH(3)SH)(n), n = 3-5, show a broad band near 2567 cm(-1) with much greater intensity. In the CH-stretching region, absorption bands of (CH(3)SH)(2) are located near 2865, 2890, 2944, and 3010 cm(-1), red-shifted by 3-5 cm(-1) from those of CH(3)SH. These red shifts increase slightly for larger clusters and bands near 2856, 2884, 2938, and 3005 cm(-1) were observed for (CH(3)SH)(5). These spectral results indicate that the S-H[middle dot][middle dot][middle dot]S hydrogen bond plays an important role in clusters with n = 3-5, but not in (CH(3)SH)(2), in agreement with theoretical predictions. The absence of a band near 2608 cm(-1) that corresponds to absorption of the non-hydrogen-bonded SH moiety and the large width of observed feature near 2567 cm(-1) indicate that the dominant stable structures of (CH(3)SH)(n), n = 3-5, have a cyclic hydrogen-bonded framework.

Infrared absorption of methanol clusters (CH3OH)n with n = 2-6 recorded with a time-of-flight mass spectrometer using infrared depletion and vacuum-ultraviolet ionization.

We investigated IR spectra in the CH- and OH-stretching regions of size-selected methanol clusters, (CH(3)OH)(n) with n = 2-6, in a pulsed supersonic jet by using the IR-VUV (vacuum-ultraviolet) ionization technique. VUV emission at 118 nm served as the source of ionization in a time-of-flight mass spectrometer. The tunable IR laser emission served as a source of predissociation or excitation before ionization. The variations of intensity of protonated methanol cluster ions (CH(3)OH)(n)H(+) and CH(3)OH(+) and (CH(3)OH)(2)(+) were monitored as the IR laser light was tuned across the range 2650-3750 cm(-1). Careful processing of these action spectra based on photoionization efficiencies and the production and loss of each cluster due to photodissociation yielded IR spectra of the size-selected clusters. Spectra of methanol clusters in the OH region have been extensively investigated; our results are consistent with previous reports, except that the band near 3675 cm(-1) is identified as being associated with the proton acceptor of (CH(3)OH)(2). Spectra in the CH region are new. In the region 2800-3050 cm(-1), bands near 2845, 2956, and 3007 cm(-1) for CH(3)OH split into 2823, 2849, 2934, 2955, 2984, and 3006 cm(-1) for (CH(3)OH)(2) that correspond to proton donor and proton acceptor, indicating that the methanol dimer has a preferred open-chain structure. In contrast, for (CH(3)OH)(3), the splitting diminishes and the bands near 2837, 2954, and 2987 cm(-1) become narrower, indicating a preferred cyclic structure. Anharmonic vibrational wavenumbers predicted for the methanol open-chain dimer and the cyclic trimer with the B3LYP∕VPT2∕ANO1 level of theory are consistent with experimental results. For the tetramer and pentamer, the spectral pattern similar to that of the trimer but with greater widths was observed, indicating that the most stable structures are also cyclic.

Infrared absorption of gaseous ClCS detected with time-resolved Fourier-transform spectroscopy.

A transient infrared absorption spectrum of gaseous ClCS was detected with a step-scan Fourier-transform spectrometer coupled with a multipass absorption cell. ClCS was produced upon irradiating a flowing mixture of Cl2CS and N2 or CO2 with a KrF excimer laser at 248 nm. A transient band in the region of 1160-1220 cm-1, which diminished on prolonged reaction, is assigned to the C-S stretching (nu1) mode of ClCS. Calculations with density-functional theory (B3P86 and B3LYP/aug-cc-pVTZ) predict the geometry, vibrational wave numbers, and rotational parameters of ClCS. The rotational contour of the spectrum of ClCS simulated based on predicted rotational parameters agrees satisfactorily with experimental observation; from spectral simulation, the band origin is determined to be at 1194.4 cm-1. Reaction kinetics involving ClCS, CS, and CS2 are discussed.