Prokaryotic maintenance respiration and associated metabolic activities constitute a considerable proportion of the total respiration of carbon to CO2 in the ocean's mixed layer. However, seasonal influences on prokaryotic maintenance activities in terms of morphological and metabolic adaptations at low (winter) and high productivity (summer) are still unclear. To address this, we examined the natural prokaryotic communities at the mesocosm scale to analyse the differences in their morphological features and gene expression at low and high maintenance respiration, experimentally manipulated with the specific growth rate. Here, we showed that morphological features including membrane blebbing, membrane vesicles, and cell‒cell connections occurred under high productivity. Metabolic adaptations associated with maintenance activities were observed under low productivity. Several Kyoto Encyclopedia of Genes and Genomes categories related to signal transduction, energy metabolism, and translational machinery supported maintenance activities under simulated winter conditions. Differential abundances of genes related to transporters, osmoregulation, nitrogen metabolism, ribosome biogenesis, and cold stress were observed. Our results demonstrate how specific growth rate in different seasons can influence resource allocation at the levels of morphological features and metabolic adaptations. This motivates further study of morphological features and their ecological role during high productivity, while investigations of metabolic adaptations during low productivity can advance our knowledge about maintenance activities.
Scanning electron microscopy (SEM) can reveal the ultrastructure of bacterial spores, including morphology, surface features, texture, spore damage, germination, and appendages. Understanding these features can provide a basis for adherence, how physical and environmental stressors affect spore viability, integrity, and functionality, as well as the distribution and function of surface appendages. However, the spore sample preparation method can significantly impact the SEM images' appearance, resolution, and overall quality. In this study, we compare different spore preparation methods to identify optimal approaches for preparation time, spore appearance and resolved features, including the exosporium and spore pili, for SEM imaging. We use Bacillus paranthracis as model species and evaluate the efficacy of preparation protocols using different fixation and drying methods, as well as imaging under room- and cryogenic temperatures. We compare and assess method complexity to the visibility of the spore exosporium and spore appendages across different methods. Additionally, we use Haralick texture features to quantify the differences in spore surface appearance and determine the most suitable method for preserving spore structures and surface features during SEM evaluation. The findings from this study will help establish protocols for preparing bacterial spores for SEM and facilitating accurate and reliable analysis of spores' characteristics.
The biopolymer lignin is deposited in the cell walls of vascular cells and is essential for long-distance water conduction and structural support in plants. Different vascular cell types contain distinct and conserved lignin chemistries, each with specific aromatic and aliphatic substitutions. Yet, the biological role of this conserved and specific lignin chemistry in each cell type remains unclear. Here, we investigated the roles of this lignin biochemical specificity for cellular functions by producing single cell analyses for three cell morphotypes of tracheary elements, which all allow sap conduction but differ in their morphology. We determined that specific lignin chemistries accumulate in each cell type. Moreover, lignin accumulated dynamically, increasing in quantity and changing in composition, to alter the cell wall biomechanics during cell maturation. For similar aromatic substitutions, residues with alcohol aliphatic functions increased stiffness whereas aldehydes increased flexibility of the cell wall. Modifying this lignin biochemical specificity and the sequence of its formation impaired the cell wall biomechanics of each morphotype and consequently hindered sap conduction and drought recovery. Together, our results demonstrate that each sap-conducting vascular cell type distinctly controls their lignin biochemistry to adjust their biomechanics and hydraulic properties to face developmental and environmental constraints.
Lignins, abundant phenolic cell wall polymers that accumulate in vascular tissue, were essential for plant terrestrialization as they enable sap conduction and mechanical support. Although lignification is currently understood as a random process, different cell types accumulate lignins with different compositions. The biological significance of these cellular differences is however still unknown. We performed single cell analyses to decipher the specific roles of different lignins and their residues on sap conduction and mechanical strengthening in plant xylem, using inducible pluripotent cell cultures and genetically modified whole plants. We show that specific lignins dynamically accumulate in each cell type and their morphotypes using distinct genetic programs, and that different lignin residues have non-redundant roles on plant biomechanical and hydraulic properties. Lignin is therefore a dynamic polymer changing composition to tailor the load bearing and sap conduction properties of each cells, in order for plants to adapt to developmental and environmental constraints.
Glendonites have been found worldwide in marine sediments from the Neoproterozoic Era to the Quaternary Period. The precursor of glendonite, ikaite (CaCO3 · 6H2O), is metastable and has only been observed in nature at temperatures <7 °C. Therefore, glendonites in the sedimentary record are commonly used as paleotemperature indicators. However, several laboratory experiments have shown that the mineral can nucleate at temperatures>7 °C. Here we investigate the nucleation range for ikaite as a function of temperature and pH. We found that ikaite precipitated at temperatures of at least 35 °C at pH 9.3 −10.3 from a mixture of natural seawater and sodium carbonate rich solution. At pH 9.3, we observed pseudomorphic replacement of ikaite by porous calcite during the duration of the experiment (c. 5 hours). These results imply that ikaite can form at relatively high temperatures but will then be rapidly replaced by a calcite pseudomorph. This finding challenges the use of glendonites as paleotemperature indicators.
Herein, we report the synthesis of a highly active and mesoporous Bronsted acidic NbOPO4/SBA-15 catalyst. The prepared catalysts were thoroughly characterized by means of analytical techniques such as XRD, FT-IR, XPS, NH3-TPD, SEM-EDS, TEM, TGA, P-31-MAS-NMR and N-2-physisorption. The H3PO4 free deposition method was found to be effective for preserving the structure of Silica based carrier. In terms of catalytic performance, these materials demonstrated high activity upon C-C coupling of 2-methyl furan with carbonyl compounds and out-performing bulk NbOPO4, Nb2O5/SBA-15 and traditional solid acid catalysts (Al-MCM-41, Si/Al and H-ZSM-5). The NbOPO4/SBA-15 catalysts were stable and maintained high activity upon reuse and continuous operation (similar to 65 h). Furthermore, the Pd loaded counterparts (Pd/NbOPO4/SBA-15 and Pd/Nb2O5/SBA-15) also functioned as bifunctional catalysts and exhibited excellent activity upon subsequent hydrodeoxygenation of C-C coupling products. Most importantly, in terms of jet-fuel range hydrocarbons selectivity, these catalysts outperformed monofunctional Pd/carbon and aluminosilicate based bifunctional catalysts.
Earth-abundant cobalt-doped hematite thin-film electrocatalysts were explored for acidic water oxidation. The strategically doped hematite produced a stable geometric current density of 10 mA cm-2 for up to 50 h at pH 0.3, as a result of Co-enhanced intrinsic catalytic activity and charge transport properties across the film matrix.
BACKGROUND:Immunogold labeling in combination with transmission electron microscopy analysis is a technique frequently used to correlate high-resolution morphology studies with detailed information regarding localization of specific antigens. Although powerful, the methodology has limitations and it is frequently difficult to acquire a stringent system where unspecific low-affinity interactions are removed prior to analysis.RESULTS:We here describe a combinatorial strategy where surface plasmon resonance and immunogold labeling are used followed by a direct analysis of the sensor-chip surface by scanning electron microscopy. Using this approach, we have probed the interaction between amyloid-β fibrils, associated to Alzheimer's disease, and apolipoprotein E, a well-known ligand frequently found co-deposited to the fibrillar form of Aβ in vivo. The results display a lateral binding of ApoE along the amyloid fibrils and illustrates how the gold-beads represent a good reporter of the binding.CONCLUSIONS:This approach exposes a technique with generic features which enables both a quantitative and a morphological evaluation of a ligand-receptor based system. The methodology mediates an advantage compared to traditional immunogold labeling since all washing steps can be monitored and where a high stringency can be maintained throughout the experiment.
We demonstrate the use of Scanning Electron microscopy (SEM) in combination with Surface Plasmon Resonance (SPR) to probe and verify the formation of amyloid and its morphology on an SPR chip. SPR is a technique that measures changes in the immobilized weight on the chip surface and is frequently used to probe the formation and biophysical properties of amyloid structures. In this context it is of interest to also monitor the morphology of the formed structures. The SPR chip surface is made of a layer of gold, which represent a suitable material for direct analysis of the surface using SEM. The standard SPR chip used here (CM5-chip, GE Healthcare, Uppsala, Sweden) can easily be disassembled and directly analyzed by SEM. In order to verify the formation of amyloid fibrils in our experimental conditions we analyzed also in-solution produced structures by using Transmission Electron Microscopy (TEM). For further details and experimental findings, please refer to the article published in Journal of Molecular Biology, (Brännström K. et al., 2018) [1].
Fibril formation of the amyloid-β peptide (Aβ) follows a nucleation-dependent polymerization process and is associated with Alzheimer's disease. Several different lengths of Aβ are observed in vivo, but Aβ1–40 and Aβ1–42 are the dominant forms. The fibril architectures of Aβ1–40 and Aβ1–42 differ and Aβ1–42 assemblies are generally considered more pathogenic. We show here that monomeric Aβ1–42 can be cross-templated and incorporated into the ends of Aβ1–40 fibrils, while incorporation of Aβ1–40 monomers into Aβ1–42 fibrils is very poor. We also show that via cross-templating incorporated Aβ monomers acquire the properties of the parental fibrils. The suppressed ability of Aβ1–40 to incorporate into the ends of Aβ1–42 fibrils and the capacity of Aβ1–42 monomers to adopt the properties of Aβ1–40 fibrils may thus represent two mechanisms reducing the total load of fibrils having the intrinsic, and possibly pathogenic, features of Aβ1–42 fibrils in vivo. We also show that the transfer of fibrillar properties is restricted to fibril-end templating and does not apply to cross-nucleation via the recently described path of surface-catalyzed secondary nucleation, which instead generates similar structures to those acquired via de novo primary nucleation in the absence of catalyzing seeds. Taken together these results uncover an intrinsic barrier that prevents Aβ1–40 from adopting the fibrillar properties of Aβ1–42 and exposes that the transfer of properties between amyloid-β fibrils are determined by their path of formation.
Stable and efficient oxygen evolution reaction (OER) catalysts for the oxidation of water to dioxygen in highly acidic media are currently limited to expensive noble metal (Ir and Ru) oxides since presently known OER catalysts made of inexpensive earth-abundant materials generally suffer anodic corrosion at low pH. In this study, we report that a mixed-polymorph film comprising maghemite and hematite, prepared using spray pyrolysis deposition followed by low-temperature annealing, showed a sustained OER rate (>24 h) corresponding to a current density of 10 mA cm(-2) at an initial overpotential of 650 mV, with a Tafel slope of only 56 mV dec(-1) and near-100% Faradaic efficiency in 0.5 M H2SO4 (pH 0.3). This performance is remarkable, since iron (III) oxide films comprising only maghemite were found to exhibit a comparable intrinsic activity, but considerably lower stability for OER, while films of pure hematite were OER-inactive. These results are explained by the differences in the polymorph crystal structures, which cause different electrical conductivity and surface interactions with water molecules and protons. Our findings not only reveal the potential of iron (III) oxide as acid-stable OER catalyst, but also highlight the important yet hitherto largely unexplored effect of crystal polymorphism on electrocatalytic OER performance. (C) 2018 Elsevier Inc. All rights reserved.
Hydrated clay minerals that are common to Earth's atmosphere and terrestrial and aquatic environments can form gels that host saline solutions. Using cryogenic electron microscopy and vibration spectroscopy, we show that saline gels of montmorillonite frozen at < -90 degrees C host elongated hexagonal ice (I-h) microcrystals embedded in a network of honeycomb micropores. Freezing segregates salts into walls of aggregated clay nanoparticles sharing face-to-face contacts. Above similar to -50 degrees C, clay gels that are sufficiently dense (>> 10 g/L) and flexible (Na-exchanged montmorillonite) also host the cryosalt mineral hydrohalite (NaCl center dot 2H(2)O), either co-existing or entirely replacing I-h in the gels. Hydrohalite does not form in gels of low-density (<10 g/L) or rigid (Ca-exchange montmorillonite) clay particles. These results suggest that hydrohalite forms in expandable clay gels that are sufficiently dense and flexible to retain saline solutions within their walls, possibly through interparticle capillary and hydration forces. These forces effectively oppose water diffusion to growing ice microcrystals within micropores, thus prolonging the lifetime of hydrohalite within these hydrated clay gels. Our findings tie the fate of ice and cryosalt nucleation and growth to the water-retention capability of expandable clay gels.
The development of efficient, durable, and inexpensive hydrogen evolution electrodes remains a key challenge for realizing a sustainable H-2 fuel production via electrocatalytic water splitting. Herein, nickel-iron phosphide porous films with precisely controlled metal content were synthesized on Ti foil using a simple and scalable two-step strategy of spray-pyrolysis deposition followed by low-temperature phosphidation. The nickel-iron phosphide of an optimized Ni:Fe ratio of 1:4 demonstrated excellent overall catalytic activity for hydrogen evolution reaction (HER) in 0.5 M H2SO4, achieving current densities of -10 and -30 mA cm(-2) at overpoteritials of 101 and 123 mV, respectively, with a Tafel slope of 43 mV dec(-1). Detailed analysis obtained by X-ray diffraction, electron microscopy, electrochemistry, and X-ray photoelectron spectroscopy revealed that the superior overall HER activity of nickel iron phosphide as compared to nickel phosphide and iron phosphide was a combined effect of differences in the morphology (real surface area) and the intrinsic catalytic properties (electronic structure). Together with a long-term stability and a near-100% Faradaic efficiency, the nickel-iron phosphide electrodes produced in this study provide blueprints for large-scale H-2 production.
Oxygen evolution catalysts (OEC) are often employed on the surface of photoactive, semiconducting photoanodes to boost their kinetics and stability during photoelectrochemical water oxidation. However, the necessity of using optically transparent OEC to avoid parasitic light absorption by the OEC under front-side illumination is often neglected. Here, we show that furnishing the surface of a WO3 photoanode with suitable loading of FeOOH as a transparent OEC improved the photocurrent density by 300% at 1 V versus RHE and the initial photocurrent-to-O-2 Faradaic efficiency from similar to 70 to similar to 100%. The data from the photo-voltammetry, electrochemical impedance, and gas evolution measurements these improvements were a combined result of reduced hole-transfer resistance for water oxidation, minimized surface recombination of charge carriers, and improved stability against photocorrosion of WO3. We demonstrate the utility of transparent FeOOH-coated W(O)3 in a solar-powered, tandem water-splitting device by combining it with a double-junction Si solar cell and a Ni-Mo hydrogen evolution catalyst. This device performed at a solar-to-hydrogen conversion efficiency of 1.8% in near-neutral K2SO4 electrolyte.
This thesis work describes the fabrication and surface enhanced Raman spectroscopy (SERS) characterization of vertically aligned nitrogen (N) doped multi walled carbon nanotube (MWCNT) forests coated by silver (Ag) and gold (Au) nanoparticles. In the present work, the CNT forests were grown from a catalyst metal layer by the chemical vapor deposition (CVD) process at temperature of 800 C and a physical vapor deposition (PVD) and annealing processes were applied subsequently for the evaporation and diffusion of noble metal nanoparticles on the forest. Transistor patterning of 20, 50 and 100 μm were made onto the silicon-oxide (SiO2) wafers through the photolithography process with and without depositing a thickness of 10 nm titanium (Ti) buffer layer on the Si-surfaces. Iron (Fe) and cobalt (Co) were used together to deposite a thickness of 5 nm catalyst layer onto the Single Side Polished (SSP) wafers. As carbon and nitrogen precursor for the CNT growth was used pyridine. Two different treatment times (20 and 60 minutes) in the CVD process determined the CNT forest height. Scanning Electron Microscopy (SEM) imaging was employed to characterize the CNT forest properties and Ag and Au nanoparticle distribution along the CNT walls. The existence of “hot spots” created by the Ag and Au nanoparticles through the surface roughness and plasmonic properties was demonstrated by the SERS measurements. Accordingly, the peak intensity at wave number of 1076 cm was picked up from each SERS spectra to establish the Agand Au-trend curves with different concentrations of 4-ATP solution. The SERS mapping was also carried out to study the Agand Au-coated CNT surface homogeneity and “hot spots” distribution on the CNT surface. The SERS enhancement factors (EF ) were calculated by applying an analyte solution of ethanolic 4-ATP on the CNT surface. The calculated values of EF from Agand Au-coated CNT forests were 9×10 and 2.7×10 respectively.