Single Repeat Unit Research Articles

Wide‐Bandgap Polymers with a C(sp3)─F Polyfluoride Backbone Enable High‐Efficient Ternary Organic Solar Cells

AbstractFluorination strategy is demonstrated to be a successful approach for optimizing the electron distribution and morphology of organic photovoltaic materials. The previous works focus on introducing only a few C(sp2)─F bonds into conjugated backbone or C(sp3)─F bonds into sidechains. Herein, a new strategy by introducing C(sp3)─F polyfluoride unit into the backbone is proposed, wherein the fluorine atoms are not involved into the conjugation but can promote the intermolecular interaction between backbones. Two wide‐bandgap fluoropolymers are prepared and employed as the third component for ternary organic solar cells. As expected, even if there are six fluorine atoms in a single repeat unit, the relevant fluoropolymers possess complementary absorption and aligned energy levels. More importantly, the polyfluoride backbone affords adequate non‐covalent interactions, consequently enhancing the polymer aggregation and packing order, which is verified by a fibril‐like morphology in the blend film with the host polymer PM6 and only 10 wt.% fluoropolymer. In addition, the decreased surface energy caused by polyfluoride unit is beneficial for the improvement of domain purity and the formation of nanoscale phase separation between donor and acceptor materials. As a result, the fluoropolymer‐assisted ternary device displays a higher efficiency of 18.74% compared with the binary device (17.39%).

Characterization and visualization of tandem repeats at genome scale.

Tandem repeat (TR) variation is associated with gene expression changes and numerous rare monogenic diseases. Although long-read sequencing provides accurate full-length sequences and methylation of TRs, there is still a need for computational methods to profile TRs across the genome. Here we introduce the Tandem Repeat Genotyping Tool (TRGT) and an accompanying TR database. TRGT determines the consensus sequences and methylation levels of specified TRs from PacBio HiFi sequencing data. It also reports reads that support each repeat allele. These reads can be subsequently visualized with a companion TR visualization tool. Assessing 937,122 TRs, TRGT showed a Mendelian concordance of 98.38%, allowing a single repeat unit difference. In six samples with known repeat expansions, TRGT detected all expansions while also identifying methylation signals and mosaicism and providing finer repeat length resolution than existing methods. Additionally, we released a database with allele sequences and methylation levels for 937,122 TRs across 100 genomes.

Living Alternating Ring-Opening Metathesis Copolymerization of 2,3-Dihydrofuran to Provide Completely Degradable Polymers.

2,3-Dihydrofuran (DHF) has recently been gaining significant attention as a comonomer in metathesis polymerization, thanks to its ability to provide the resultant polymer backbones with stimuli-responsive degradability. In this report, we present living alternating copolymerization of DHF with less reactive endo-tricyclo[4.2.2.02,5 ]deca-3,9-dienes (TDs) and endo-oxonorbornenes (oxoNBs). By carefully controlling the reactivity of both the Ru initiators and the monomers, we have achieved outstanding A, B-alternation (up to 98 %) under near stoichiometric DHF loading conditions. Notably, we have also found that the use of a more sterically hindered Ru initiator helps to attain polymer backbones with higher DHF incorporation and superior A, B-alternation. While preserving the living characteristics of DHF copolymerization, as evidenced by controlled molecular weights (up to 73.9 kDa), narrow dispersities (down to 1.05), and block copolymer formation, our DHF copolymers could be broken down to a single repeat unit level under acidic conditions. 1 H NMR analysis of the model copolymer revealed that after 24 hours of degradation, up to 80 % of the initial polymer was transformed into a single small molecule product, and after purification, up to 66 % of the degradation product was retrieved. This study provides a versatile approach to improve the alternation and degradability of DHF copolymers.

Living Alternating Ring‐Opening Metathesis Copolymerization of 2,3‐Dihydrofuran to Provide Completely Degradable Polymers

Abstract2,3‐Dihydrofuran (DHF) has recently been gaining significant attention as a comonomer in metathesis polymerization, thanks to its ability to provide the resultant polymer backbones with stimuli‐responsive degradability. In this report, we present living alternating copolymerization of DHF with less reactive endo‐tricyclo[4.2.2.02,5]deca‐3,9‐dienes (TDs) and endo‐oxonorbornenes (oxoNBs). By carefully controlling the reactivity of both the Ru initiators and the monomers, we have achieved outstanding A, B‐alternation (up to 98 %) under near stoichiometric DHF loading conditions. Notably, we have also found that the use of a more sterically hindered Ru initiator helps to attain polymer backbones with higher DHF incorporation and superior A, B‐alternation. While preserving the living characteristics of DHF copolymerization, as evidenced by controlled molecular weights (up to 73.9 kDa), narrow dispersities (down to 1.05), and block copolymer formation, our DHF copolymers could be broken down to a single repeat unit level under acidic conditions. 1H NMR analysis of the model copolymer revealed that after 24 hours of degradation, up to 80 % of the initial polymer was transformed into a single small molecule product, and after purification, up to 66 % of the degradation product was retrieved. This study provides a versatile approach to improve the alternation and degradability of DHF copolymers.

Electrochemical Model for a Three-Electrode Lead Acid Cell: Boundary Conditions for Asymmetric Configurations

A one-dimensional (1D) electrochemical model is developed for a lead-acid demonstration cell comprising two positive electrodes engaging a single negative electrode. Classical 1D models, which analyze a single repeat unit in a full battery, are extended to this non-standard configuration by considering additional porous electrode and electrolyte reservoir domains. The non-standard model necessitates appropriate boundary conditions to couple electrochemical variables in different domains, since symmetry boundary conditions typically employed at the current collector grids are no longer applicable. The modified model, with new boundary conditions, is simulated using standard techniques. Salient modeling and simulation differences compared to a standard lead-acid model are discussed, as are trends in predicted variables. The non-standard model predicts reduced polarization and more uniform utilization of the non-limiting electrodes, in addition to non-zero reaction currents and active material utilization in the terminal electrode faces, which are typically ignored in “unit-cell” analyses. This model is expected to be of substantial utility in guiding evaluations of new lead-acid battery designs through improved prediction of performance of such test configurations. The boundary conditions introduced herein are also useful for 1D modeling of non-standard configurations characterized by multiple, electrochemically interacting porous domains, particularly where spatial current distributions are initially unknown.

Towards an Impedance-Based Analysis of SOFC-Stacks

To understand the performance and durability limitations in SOFC stacks and systems, impedance spectroscopy is becoming increasingly important. However, in the analysis of entire stacks, gradients over the active cell area are averaged out, preventing access to local phenomena.To get better insight into the spatial distribution of performance losses in a stack layer, incremental cells and repeat units with an active electrode area of 1 cm² are investigated in this study.Impedance spectroscopy and the subsequent impedance data analysis by the distribution of relaxation times (DRT) is applied to deconvolute the polarization processes in the Ni/CGO fuel electrode and the LSM air electrode of the investigated electrolyte supported cell. To ensure an appropriate deconvolution of air and fuel electrode processes, next to full cells symmetrical anode and cathode cells are applied. In case of Ni/CGO fuel electrodes charge transfer and gas diffusion overlap in the spectrum and the assignment has to be done indirectly using inert gas mixtures [1].In Figure 1 impedance spectra and DRTs of fuel and air electrode obtained from symmetrical cells are compared with the full cell spectrum. This analysis enables a clear allocation of the processes in the single cell to Ni/CGO fuel electrode and LSM air electrode.Next to the cell testing in an inert, ideal environment namely an Al2O3 flow field with gold and nickel contact grids respectively, the study is expanded to stack like conditions. The additional losses due to contact resistances and gas supply limitations are studied similar to Kornely et al. [2] for single repeat units (single cell + contact layer + metallic interconnects). In this contribution a physio-chemical equivalent circuit model based on these measurements will be presented and the complex impedance behavior of single cells and repeat units will be discussed.

Realizing the Lowest Bandgap and Exciton Binding Energy in a Two-Dimensional Lead Halide System.

Finding stable analogues of three-dimensional (3D) lead halide perovskites has motivated the exploration of an ever-expanding repertoire of two-dimensional (2D) counterparts. However, the bandgap and exciton binding energy in these 2D systems are generally considerably higher than those in 3D analogues due to size and dielectric confinement. Such quantum confinements are most prominently manifested in the extreme 2D realization in (A)mPbI4 (m = 1 or 2) series of compounds with a single inorganic layer repeat unit. Here, we explore a new A-site cation, 4,4'-azopyridine (APD), whose size and hydrogen bonding properties endow the corresponding (APD)PbI4 2D compound with the lowest bandgap and exciton binding energy of all such compounds, 2.19 eV and 48 meV, respectively. (APD)PbI4 presents the first example of the ideal Pb-I-Pb bond angle of 180°, maximizing the valence and conduction bandwidths and minimizing the electron and hole effective masses. These effects coupled with a significant increase in the dielectric constant provide an explanation for the unique bandgap and exciton binding energies in this system. Our theoretical results further reveal that the requirement of optimizing the hydrogen bonding interactions between the organic and the inorganic units provides the driving force for achieving the structural uniqueness and the associated optoelectronic properties in this system. Our preliminary investigations in characterizing photovoltaic solar cells in the presence of APD show encouraging improvements in performances and stability.

Decomposing mosaic tandem repeats accurately from long reads.

Over the past 30 years, extended tandem repeats (TRs) have been correlated with approximately 60 diseases with high odds ratios, and most known TRs consist of single repeat units. However, in the last few years, mosaic TRs composed of different units have been found to be associated with several brain disorders by long-read sequencing techniques. Mosaic TRs are difficult-to-characterize sequence configurations that are usually confirmed by manual inspection. Widely used tools are not designed to solve the mosaic TR problem and often fail to properly decompose mosaic TRs. We propose an efficient algorithm that can decompose mosaic tandem repeats in the input string with high sensitivity. Using synthetic benchmark data, we demonstrate that our program named uTR outperforms TRF and RepeatMasker in terms of prediction accuracy, this is especially true when mosaic TRs are more complex, and uTR is faster than TRF and RepeatMasker in most cases. The software program uTR that implements the proposed algorithm is available at https://github.com/morisUtokyo/uTR.

A multiscale model validated on local current measurements for understanding the solid oxide cells performances

A physical-based model has been developed and validated to unravel the complex relationships between the global solid oxide cells response and the reaction mechanisms taking place in the electrodes. This numerical tool combines three length-scales modules from the electrode microstructure up to the single repeat unit. This model allows computing the local distribution of reaction kinetic rates, current densities, and gas composition as function of the cell operating conditions. To validate the multiscale model, a special experimental setup has been developed to measure the local polarization curves along the cell length. For this purpose, a specific design of the interconnect has been proposed in order to probe the local current density on standard cells. A good agreement has been found between the experimental and simulated data for different operating conditions. The fully validated model has been used to analyze the cell operation in electrolysis and fuel cell modes. The activated reaction pathways associated with the elementary steps in the active layers have been investigated depending on the position along the cell length.

Discovery and characterization of a new class of O-linking oligosaccharyltransferases from the Moraxellaceae family.

Bacterial protein glycosylation is commonly mediated by oligosaccharyltransferases (OTases) that transfer oligosaccharides en bloc from preassembled lipid-linked precursors to acceptor proteins. Natively, O-linking OTases usually transfer a single repeat unit of the O-antigen or capsular polysaccharide to the side chains of serine or threonine on acceptor proteins. Three major families of bacterial O-linking OTases have been described: PglL, PglS, and TfpO. TfpO is limited to transferring short oligosaccharides both in its native context and when heterologously expressed in glycoengineered Escherichia coli. On the other hand, PglL and PglS can transfer long-chain polysaccharides when expressed in glycoengineered E. coli. Herein, we describe the discovery and functional characterization of a novel family of bacterial O-linking OTases termed TfpM from Moraxellaceae bacteria. TfpM proteins are similar in size and sequence to TfpO enzymes but can transfer long-chain polysaccharides to acceptor proteins. Phylogenetic analyses demonstrate that TfpM proteins cluster in distinct clades from known bacterial OTases. Using a representative TfpM enzyme from Moraxella osloensis, we determined that TfpM glycosylates a C-terminal threonine of its cognate pilin-like protein and identified the minimal sequon required for glycosylation. We further demonstrated that TfpM has broad substrate tolerance and can transfer diverse glycans including those with glucose, galactose, or 2-N-acetyl sugars at the reducing end. Last, we find that a TfpM-derived bioconjugate is immunogenic and elicits serotype-specific polysaccharide IgG responses in mice. The glycan substrate promiscuity of TfpM and identification of the minimal TfpM sequon renders this enzyme a valuable additional tool for expanding the glycoengineering toolbox.

Mutational analysis of 16 STR markers in the Slovak population

Background Short tandem repeats (STRs) are genetic markers frequently used for human identification and paternity testing. They are highly mutable, which may occasionally lead to inconsistencies between the genotypes of parents and their children. As the mutation rates of individual STR markers can vary among populations, population-specific data are of high importance. Aim To investigate the mutation rates of 16 STR markers in the Slovak population. Subjects and methods In this study, we analysed the germline mutation rates of 16 STR markers (TH01, D3S1358, vWA, D21S11, D16S539, D1S1656, D19S433, SE33, D10S1248, D22S1045, D12S391, D8S1179, D2S1338, D2S441, D18S51 and FGA) in the Slovak population. At these loci, we analysed 42 096 allelic transfers and identified 61 mutation events. Results The loci with the highest overall mutation rates were SE33 and FGA, while no mutations were identified in TH01, D19S433 and D22S1045. The average paternal mutation rate was higher than the maternal mutation rate. All but one mutation consisted of gains or losses of a single repeat unit and the overall mutation rate was estimated to be 1.45 x10−3 per meiosis. Conclusion This study provides data which can be used to further strengthen the correct paternity index calculations and reliability of paternity testing in Slovakia.

Both cis and trans-acting genetic factors drive somatic instability in female carriers of the FMR1 premutation

The fragile X mental retardation (FMR1) gene contains an expansion-prone CGG repeat within its 5′ UTR. Alleles with 55–200 repeats are known as premutation (PM) alleles and confer risk for one or more of the FMR1 premutation (PM) disorders that include Fragile X-associated Tremor/Ataxia Syndrome (FXTAS), Fragile X-associated Primary Ovarian Insufficiency (FXPOI), and Fragile X-Associated Neuropsychiatric Disorders (FXAND). PM alleles expand on intergenerational transmission, with the children of PM mothers being at risk of inheriting alleles with > 200 CGG repeats (full mutation FM) alleles) and thus developing Fragile X Syndrome (FXS). PM alleles can be somatically unstable. This can lead to individuals being mosaic for multiple size alleles. Here, we describe a detailed evaluation of somatic mosaicism in a large cohort of female PM carriers and show that 94% display some evidence of somatic instability with the presence of a series of expanded alleles that differ from the next allele by a single repeat unit. Using two different metrics for instability that we have developed, we show that, as with intergenerational instability, there is a direct relationship between the extent of somatic expansion and the number of CGG repeats in the originally inherited allele and an inverse relationship with the number of AGG interruptions. Expansions are progressive as evidenced by a positive correlation with age and by examination of blood samples from the same individual taken at different time points. Our data also suggests the existence of other genetic or environmental factors that affect the extent of somatic expansion. Importantly, the analysis of candidate single nucleotide polymorphisms (SNPs) suggests that two DNA repair factors, FAN1 and MSH3, may be modifiers of somatic expansion risk in the PM population as observed in other repeat expansion disorders.

Stack Optimization and Testing for its Integration in a rSOC-Based Renewable Energy Storage System

This work aims at developing an innovative solution for storing renewable energies, so-called “Smart Energy Hub” (SEH) developed by Sylfen, based on reversible Solid Oxide Cell (rSOC) technology. It is able to operate either in electrolysis (SOEC) mode storing excess electricity to produce hydrogen, or when energy needs exceed local production, in SOFC (solid oxide fuel cell) mode producing electricity (and heat) from hydrogen or any other hydrogenated fuel. Particularly this paper focuses on stack development and optimization, partly performed through the REFLEX project supported by European commission funding.To achieve the project’s objectives, in terms of efficiency and increase of system power density, as well as multi-stack operation, optimizing CEA stack is necessary to upgrade a stack originally designed for SOEC research purposes, to a stack reversibly operated, but also integrated as a part of module. This paper presents results of stack optimisations and integration of cells developed within the REFLEX project.First, a reduction in cell thickness of ~20 % led to adapting the stack manufacturing process parameters. Some tests, here presented, demonstrate that the stack performances were not affected by this change.Then, significant effort was devoted to air distribution at the Single Repeat Unit (SRU) scale to minimize pressure drop, undesirable for both global system efficiency and mechanical resistance of stack sealing. At the SRU scale, air path adjustment reduced the pressure drop by a factor 2; at stack scale, the performances obtained in i-V curves demonstrated reactants distributions were unchanged.Optimized cells (so called G2) developed in the frame of REFLEX project were then integrated in a short stack (5 cells vs. 25 full size) to be compared to short stack comprising regular cells produced by Elcogen. Both stacks were tested in terms of durability over more than 1000 hours at 700°C. A first period of about 800 h of operation was conducted alternating from SOFC to SOEC mode by steps of ≈100 h. During this first part, the stack was supplied by 50/50 H2O/H2 at total flow rate of 12.0 NmL/min/cm² on fuel side and air (clean and dry) on oxygen side. Stack performances were checked at each change of operating mode through i-V curves recorded at 800, 750 and 700°C.For the reference cell, durability tests were operated galvanostatic at 0.36 A/cm² in fuel cell mode and -0.51 A/cm² in electrolysis mode. The fuel utilization (FU) was respectively 42% in SOFC, and Steam Conversion (SC) 59% in SOEC. For the optimized cell, tests were carried out at 0.35 A/cm² (FU=41%), and -0.58 A/cm² (SC=67%). A second stage of more than 250h of operation consisted to alternate daily from SOEC to SOFC by cycles of respectively 8h and 16h. Finally, degradation was evaluated and despite the increase in SOEC current density during G2 cell testing, degradation rate was very similar for both cells in SOEC as well as in SOFC mode.A full size (25-cells) stack made of G2 cells was manufactured integrating the fluidic optimizations but also manifold and an electrical insulation necessary to operate stacks serially connected electrically within the REFLEX modules produced by Sylfen. The change of scale was validated by obtaining similar i-V curves recorded for 5-cells and 25-cells stacks.REFLEX Smart Energy Hub will be operated in ENVIPARK Torino using three modules comprising of four stacks each. Stack production has to be as uniform as possible and consequently, manufacturing process has to be optimized. Dispersion in performance, that results of cell production and stack manufacturing process is checked at final stage by i-V curves recording before delivery. Uniformity in production (in terms of tightness, reactant distribution and so initial electrochemical performance) is found to be satisfactory, the dispersion of median cell stack voltage over the stack production is less than the voltage dispersion observed between the whole cells at stack level.For near future needs in rSOC system, an increase of stack power density is required to both reduce the CAPEX and increase system energy efficiency. In that frame cells produced by Elcogen has an active cell area that was extended from 100 to 196 cm² and tested at stack levels of 5 and 25 cells, respectively. Enlarged stack performances are measured via i-V curves and compared to reference 100 cm² cells stacks. As difference in median cell voltage is less than 10 mV up to a current density of -1.25 V/cm² (80% SC), this paper shows that, from a mechanical and fluidic point of view, the enlarged cell were successfully integrated in full-scale stack. Figure 1

A Dynamic Multi-Scale Model for Solid Oxide Cells Validated on Local Current Measurements: Impact of Global Cell Operation on the Electrodes Reaction Mechanisms

A dynamic physically based model has been developed to unravel the complex relationships between the overall Solid Oxide Cells (SOCs) response and the reaction mechanisms taking place in the electrodes. This numerical tool combines modules for different length-scales from the electrode microstructure up to the single repeat unit. First, models have been developed to emulate digital twins of electrode microstructures made of the classical SOCs materials [1]. The microstructural properties of the active layers and the current collectors are then computed on the synthetic volumes and used as inputs in the electrochemical models. The microscale models for the active layers take into account the mass and the charge transport phenomena for the solid and gas phases. For each electrode, the proposed reaction mechanism is split in a sequence of elementary steps with different pathways that can be activated depending on the polarization [2, 3]. The electrode models are finally coupled with a macroscopic description including the cell geometry and the design of the gas channels [4]. This model allows computing the cell polarization curves, the overpotentials and the EIS together with the distribution of the local current density and gas composition in the single repeat unit. This multiscale model has been used to study a typical cell made of the classical SOCs materials: the electrolyte was in Yttria Stabilized Zirconia (YSZ) whereas the hydrogen and oxygen electrodes were respectively composed by a cermet of Nickel and YSZ (Ni-YSZ) and a composite of Lanthanum doped Strontium Cobaltite Ferrite and Ceria doped Gadolinium Oxide (LSCF-CGO). For this cell, the representativeness of the electrodes synthetic microstructures have been checked on reconstructions obtained by tomographic techniques. It has been shown that the synthetic electrodes reproduce accurately the real microstructures. Moreover, the models at the electrode level have been carefully validated on polarizations curves and Electrochemical Impedance Spectra (EIS) measured on symmetrical cells using a three-electrode setup. It is worth noting that the electrodes of the tested symmetrical cells were manufactured using the same materials and composition than the complete cell. Finally, a specific attention has been paid in this work to validate the approach with an original experimental setup allowing the measurement of the local current densities on the full cell without electrode segmentation. This setup is composed of nine symmetrical-spaced pins that perform the measurement of local polarization curves from the inlet to the cell outlet. A campaign of tests has been carried out in fuel cell and electrolysis mode with different temperatures and flow rates. A good agreement has been found between the experimental and simulated data. It has been shown that the model is able to reproduce the evolution of the local polarization curves with a higher current density at the cell inlet. Furthermore, the simulated EIS for the cell have been found to be consistent with the experimental ones. The fully validated model has been used to analyze the cell operation in electrolysis and fuel cell mode. The reaction pathways associated to the elementary steps in the active layers have been discussed depending on the position within the electrodes and the polarizations. This model will then be used to implement the degradation laws such as the Ni agglomeration and compute the loss of cell performances and the remaining useful lifetime [5]. Moreover, the model could be applied to interpret the evolution of the EIS upon operation.[1] H. Moussaoui, J. Laurencin, Y. Gavet, G. Delette, M. Hubert, P. Cloetens, T. Le Bihan, J. Debayle, Stochastic geometrical modeling of solid oxide cells electrodes validated on 3D reconstructions, Computational Materials Science. 143 (2018) 262-276.[2] F. Monaco, E. Effori, M. Hubert, E. Siebert, G. Geneste, B. Morel, E. Djurado, D. Montinaro, J. Laurencin, Electrode Kinetics of Porous Ni-3YSZ Cermet Operated in Fuel Cell and Electrolysis Modes for Solid Oxide Cell Application. Under review. [3] E. Effori, J. Laurencin, E. Da Rosa Silva, M. Hubert, T. David, M. Petitjean, L. Dessemond, E. Siebert, An elementary kinetic model for the LSCF and LSCF-CGO electrodes for solid oxide cells: impact of oxygen partial pressure and degradation on the electrode response. Under review. [4] J. Laurencin, D. Kane, G. Delette, J. Deseure, F. Lefebvre-Joud, Modelling of solid oxide steam electrolyser: Impact of the operating conditions on hydrogen production. Journal of Power Sources. 196 (2011) 2080-2093.[5] M. Hubert, J. Laurencin, P. Cloetens, B. Morel, D. Montinaro, F. Lefebvre-Joud, Impact of Nickel agglomeration on Solid Oxide Cell operated in fuel cell and electrolysis modes. Journal of Power Sources. 397 (2018) 240-251. Figure 1

High-efficiency plastome base editing in rice with TAL cytosine deaminase

High-efficiency plastome base editing in rice with TAL cytosine deaminase

A Dynamic Multi-Scale Model for Solid Oxide Cells Validated on Local Current Measurements: Impact of Global Cell Operation on the Electrodes Reaction Mechanisms

A dynamic physically based model has been developed to unravel the relationships between the overall Solid Oxide Cells response and the reaction mechanisms taking place in the electrodes. This tool combines modules at three different length-scales: electrode microstructures, active functional layers, and single repeat unit. It allows computing the cell polarization together with the distribution of the local current densities, overpotentials, and gas composition. It has been shown that the synthetic electrode model reproduces accurately the real microstructure, which has been checked by comparison with 3D reconstructions. The microscale electrode models have been validated using polarization curves and impedance spectra measured in symmetrical cells. Finally, tests were conducted at different temperatures and inlet flow rates to validate the integrated multiscale approach. For this purpose, a special setup was developed to measure the local current densities in standard cells. A good agreement was found between the experimental and simulated data.

Pantoea stewartii WceF is a glycan biofilm-modifying enzyme with a bacteriophage tailspike-like fold

Pathogenic microorganisms often reside in glycan-based biofilms. Concentration and chain length distribution of these mostly anionic exopolysaccharides (EPS) determine the overall biophysical properties of a biofilm and result in a highly viscous environment. Bacterial communities regulate this biofilm state via intracellular small-molecule signaling to initiate EPS synthesis. Reorganization or degradation of this glycan matrix, however, requires the action of extracellular glycosidases. So far, these were mainly described for bacteriophages that must degrade biofilms for gaining access to host bacteria. The plant pathogen Pantoea stewartii (P. stewartii) encodes the protein WceF within its EPS synthesis cluster. WceF has homologs in various biofilm forming plant pathogens of the Erwinia family. In this work, we show that WceF is a glycosidase active on stewartan, the main P. stewartii EPS biofilm component. WceF has remarkable structural similarity with bacteriophage tailspike proteins (TSPs). Crystal structure analysis showed a native trimer of right-handed parallel β-helices. Despite its similar fold, WceF lacks the high stability found in bacteriophage TSPs. WceF is a stewartan hydrolase and produces oligosaccharides, corresponding to single stewartan repeat units. However, compared with a stewartan-specific glycan hydrolase of bacteriophage origin, WceF showed lectin-like autoagglutination with stewartan, resulting in notably slower EPS cleavage velocities. This emphasizes that the bacterial enzyme WceF has a role in P. stewartii biofilm glycan matrix reorganization clearly different from that of a bacteriophage exopolysaccharide depolymerase.

In-situ experimental benchmarking of solid oxide fuel cell metal interconnect solutions

The progress in the diffusion of solid oxide fuel cell (SOFC) as commercial devices is not paired by literature production. Articles describing the behaviour of SOFC stacks are rare because of confidentiality reasons for commercial suppliers while research centres prefer to focus on single components or low technology readiness level research.This article aim to fill this gap presenting the analysis of three short stacks run in operative conditions for 10 000 h each. The stacks are characterized through voltage vs time curves, electron microscopy, and electrochemical impedance spectroscopy. Focus is given on the interconnect; notably on the different types of coatings, varying for composition (MnCo2O4, MnCo1.8Fe0.2O4) and deposition technique (atmospheric plasma spray-APS, physical vapour deposition-PVD, wet powder spraying-WPS). Nitriding of the steel substrate as a solution to improve the chromium retention properties is tested as well. Resultsindicate that coating deposition technique is the most important parameter, with single repeat unit (SRU) containing PVD coating showing the lowest voltage degradation rate. Commercial ferritic stainless steel K41 confirmed to be a reliable choice if coupled with a coating. Moreover, SRU containing WPS coating demonstrated to be more reliable than expected from standard area specific resistance 4-probe test.

Ionic and Nonspherical Polymer Nanoparticles in Nonpolar Solvents

A series of ionic diblock copolymer nanoparticles was prepared in a typical nonpolar solvent (n-dodecane) via polymerization-induced self-assembly (PISA). A single cationic repeat unit was incorporated into the poly(stearyl methacrylate) (PSMA) stabilizer of otherwise uncharged poly(stearyl methacrylate)–poly(benzyl methacrylate) (PSMA–PBzMA) diblock copolymer nanoparticles. By using short PSMA stabilizer blocks, it was possible to obtain nanoparticles with the range of morphologies expected (spheres, worms, and vesicles). For nanoparticles where all stabilizer chains possessed an ionic group, higher-order morphologies were obtained at lower PBzMA degrees of polymerization than corresponding uncharged particles, and the particles were electrophoretic. For nanoparticles where only a fraction of the stabilizer chains contained an ionic group, higher-order morphologies were obtained at precisely the same PBzMA degrees of polymerization, and the electrophoretic response was greater than when the shell was fully ionic. These particles with a partially ionic shell are a fascinating system, providing morphologies that can be predicted from the existing knowledge of the diblock copolymer morphology yet with the highest possible electrophoretic mobility.

The molecular structure of novel pyriform spidroin (PySp2) reveals extremely complex central repetitive region

Orb-weaving spiders produce a diversity of silk fibers throughout their entire lifecycle, and each silk type is given a specific purpose. As a dry fiber material with wet glue, pyriform silks are different from other silk fibers and make the attachment discs which are used for bonding fibers together and attaching dragline silk to other substrates. To date, only two full-length pyriform spidroin 1 (PySp1) gene sequences were identified. Here we present a novel full-length pyriform spidroin 2 (PySp2) from orb-weaving spider, Araneus ventricosus. Although the A. ventricosus PySp2 lack the long linker regions, the central repetitive region of PySp2 is more complex than PySp1 and can be classified into four types of repetitive regions including three novel repetitive sequences and one type of repetitive region that is similar to PySp1 repeats. Prediction of hydrophobicity of A. ventricosus PySp2 reveals the two new repetitive regions display strong hydrophilicity. Analysis of CD spectrum and secondary structure prediction for A. ventricosus PySp2 repeat unit reveal α-helix conformation dominates the repetitive region. Furthermore, recombinant protein-based artificial fibers show the single repeat unit is sufficient for self-assembling into silk fiber.