Labile Structures Research Articles

Steerable Structural Evolvement and Adsorption Behavior of Metastable Polyoxovanadate-Based Metal-Organic Polyhedra.

Promoting the advancement of the structure and function of metastable substances is challenging but worthwhile. In particular, how to harness the entangled state and evolution path of labile porous structures has been at the forefront of research in molecular self-assembly. In this work, the metastable structures of polyoxovanadate-based metal-organic polyhedra (VMOPs) can be manually regulated, including separation of the interlocked aggregate by a ligand-widening approach as well as transformation from a tetrahedral to capsule-like scaffold via a vertice-remodeling strategy. In these processes, intra- and intermolecular π···π and C-H···π interactions have been recognized as the primary driving forces. Besides being responsible for commanding the structural evolvement of VMOPs, such weak interactions were able to program their spatial arrangements and hence the adsorption performances for dye and iodine. The successful use of such a weak force-dominated design concept beacons a feasible route for customization of the function-oriented metastable structures. Separation and transformation of the interlocked metastable VMOPs have been achieved via the respective ligand-widening approach and vertice-remodeling strategy. Not only their structures but also adsorption features could be well regulated by such a weak force-dominated design concept.

Role of Organic Fertilizer in the Transfer of Lead to Vegetables Produced in Tropical Mountain Agroecosystems.

Understanding the relationship between the aerobic transformation of organic matter (OM) and the bioavailability of lead to plants may allow the safe application of organic fertilizers (OF) in agriculture. The present study aimed to elucidate the relationship of different OM structures with Pb, revealing the action of OF (poultry litter) on Pb dynamics, presenting the effects of OM transformations on bioavailability and transfer to vegetables produced in tropical mountain agroecosystems (TMA). The association of Pb with hydrophilic structures (CAlk-O and CAlk-di-O) during the aerobic transformation of poultry litter (PL) contributes to the increase in the water-soluble form of this metal (3.17-15.30%). The structural changes promoted by the transformation of OM, in addition to reducing the adsorption capacity of Pb in PL (Kd reduction from 1135.50 to 87.49), favor the formation of outer-sphere complexes. PL that have a more labile structure, i.e., those that are less humified, have greater affinity for Pb. The greater affinity of Pb for labile structures that are preserved in PL during OM transformations contributed to its increase and transport to edible plant parts. Considering the edible parts of vegetables grown in TMA and fertilized with fresh PL, 100% of broccoli, 91.78% of cabbage, 80.00% of tomato, 65.96% of parsley, 49.19% of lettuce, and 32.88% of cauliflower showed Pb contamination that exceeded the permitted level. Therefore, OF contributes to lead contamination of food produced in TMA, representing a risk to human health. Studies are needed to propose additional treatments for this residue before its use.

Scanning Electron Microscopy.

Scanning electron microscopy (SEM) remains distinct in its ability to allow topographical visualization of structures. Key elements to consider for successful examination of biological specimens include appropriate preparative and imaging techniques. Chemical processing induces structural artifacts during specimen preparation, and several factors need to be considered when selecting fixation protocols to reduce these effects while retaining structures of interest. Particular care for proper dehydration of specimens is essential to minimize shrinkage and is necessary for placement under the high-vacuum environment required for routine operation of standard SEMs. Choice of substrate for mounting and coating specimens can reduce artifacts known as charging, and a basic understanding of microscope settings can optimize parameters to achieve desired results. This article describes fundamental techniques and tips for routine specimen preparation for a variety of biological specimens, preservation of labile or fragile structures, immune-labeling strategies, and microscope imaging parameters for optimal examination by SEM. © 2024 The Authors. Current Protocols published by Wiley Periodicals LLC. Basic Protocol 1: Chemical preparative techniques for preservation of biological specimens for examination by SEM Alternate Protocol 1: Practical considerations for the preparation of soft tissues Alternate Protocol 2: Removal of debris from the exoskeleton of invertebrates Alternate Protocol 3: Fixation of colonies grown on agar plates Alternate Protocol 4: Stabilization of polysaccharide structures with alcian blue and lysine Alternate Protocol 5: Preparation of non-adherent particulates in solution for SEM Support Protocol 1: Application of thin layer of adhesive on substrate to improve adherence Support Protocol 2: Poly-L-lysine coating specimen substrates for improved adherence Support Protocol 3: Microwave processing of biological specimens for examination by SEM Basic Protocol 2: Critical point drying of specimens Alternate Protocol 6: Chemical alternative to critical point drying Basic Protocol 3: Sputter coating Alternate Protocol 7: Improved bulk conductivity through "OTOTO" Basic Protocol 4: Immune-labeling strategies Alternate Protocol 8: Immune-labeling internal antigens with small gold probes Alternate protocol 9: Quantum dot or fluoronanogold preparations for correlative techniques Basic Protocol 5: Exposure of internal structures by mechanical fracturing Basic Protocol 6: Exposure of internal structures of tissues by fracturing with liquid nitrogen Basic Protocol 7: Anaglyph production from stereo pairs to produce 3D images.

Predicting Organometallic Intermediates in the Surface-Assisted Ullmann Coupling of Chrysene Isomers.

On-surface polymerization of functional organic molecules has been recently recognized as a promising route to persistent low-dimensional structures with tailorable properties. In this contribution, using the coarse-grained Monte Carlo simulation method, we study the initial stage of the Ullmann coupling of doubly halogenated chrysene isomers adsorbed on a catalytically active (111) crystalline surface. To that end, we focus on the formation of labile metal-organic precursor structures preceding the covalent bonding of chrysene monomers. Four monomeric chrysene units with differently distributed halogen substituents were probed in the simulations, and the resulting precursor structures were compared and quantified. Moreover, the effect of (pro)chirality of chrysene tectons on the structure formation was elucidated by running separate simulations in enantiopure and racemic systems. The calculations showed that suitable manipulation of the halogen substitution pattern allows for the creation of diverse precursor architectures, ranging from straight and winded chains to cyclic oligomers with enantiopure, racemic, and nonracemic composition. The obtained findings can be helpful in developing synthetic strategies for covalent polymers with predefined architecture and functionality.

Epilepsy with PCDH19 mutation: polypharmacy as a consequence of the complexity and diversity of pathogenesis mechanisms

Mutations in the human PCDH19 gene lead to epileptic encephalopathy of early childhood. It is characterized by the early onset of serial seizures, cognitive impairment and behavioral disorders (including autistic personality traits). In most cases, difficulties arise in selecting therapy due to pharmacoresistance. The pathogenesis of the disease is complex. The data available to us at the moment from numerous studies present the pathogenesis of «PCDH19 syndrome» as multi-level, affecting both the epigenetic support of cell life, and development of stem cells and progenitor cells in the process of neuroontogenesis, and the influence on the neurotransmitter mechanisms of the brain, and disruption of the formation of neural networks with an inevitable increase in the excitability of the cerebral cortex as a whole, and local changes in the highly labile regulatory structures of the hippocampal region. And it is not surprising that all these changes entail not only (and perhaps not so much) epileptization, but a profound disruption of the regulation of brain activity, accompanied by autism spectrum disorders, more profound disorders in the form of schizophrenia or cyclothymia, and the formation of delayed psychomotor development. A «side branch» of these pathogenetic processes can also be considered the participation of PCDH19 dysfunctions in certain variants of oncogenesis. The need for polypharmacy (in most cases) confirms the diversity of mechanisms involved in the pathogenesis of the disease and makes the prospects for the development of effective and rational treatment regimens very vague. Cautious optimism is caused only by attempts at relatively specific treatment with ganaxolone.

Effects of Long-Term Management on Soil Organic Carbon in Tropical Peatlands

Objective: The aim of this study was to evaluate the effects of Histosols management on soil organic matter (SOM) characteristics. Theoretical framework: Histosols are soils that provide ecosystem services, especially carbon stocks. Among the environments in which these soils are formed, peatlands stand out. The conversion of these areas into agricultural systems requires soil drainage. This practice causes reductions in carbon content and changes in the structure of the SOM. Methodology: The study was conducted in the municipality of Rio de Janeiro, Brazil. The soils were classified as Histosols. Three areas were selected: a) cassava (Manihot esculenta) cultivation for 80 years; b) forest fragment for 20 years; c) consortium of coconut palm (Cocos nucifera) and cassava for 20 years. Total organic carbon (TOC); particulate organic carbon (COP); organic carbon associated with minerals (COam); fulvic acid fraction carbon (CAF); humic acid fraction carbon (CAH) and; humin fraction carbon (CHUM) were determined. Solid-state spectroscopy (UV-vis, ATR-FTIR and 13C NMR CP/MAS) was carried out to characterize the structure of the SOM. Results and conclusion: The results showed that management and drainage have an impact on the TOC content, fractions and chemical structure of the SOM. The management adopted in the cassava area had an impact on the labile and humified fractions of the SOM. Spectroscopy showed that labile structures were lost in the humic acids (HA), while in the forest area only recalcitrant structures were preserved. Research implications: The conversion of Histosols to agricultural production using the drainage technique promotes quantitative and qualitative changes in SOM in the long term. In order to reduce greenhouse gas emissions, it is necessary to use techniques that promote carbon stocks in the soil. Originality/value: This study uses spectroscopic and chemometric techniques to highlight the effects of long-term soil management on the chemical structure of the SOM and to quantify the total carbon content and SOM fractions.

Oxidative regulation of TDP-43 self-association by a β-to-α conformational switch

An evolutionarily conserved region of the TDP-43 low-complexity domain (LCD) twenty residues in length can adopt either an α-helical or β-strand conformation. When in the latter conformation, TDP-43 self-associates via the formation of a labile, cross-β structure. Self-association can be monitored via the formation of phase-separated protein droplets. Exposure of droplets to hydrogen peroxide leads to oxidation of conserved methionine residues distributed throughout the LCD. Oxidation disassembles the cross-β structure, thus eliminating both self-association and phase separation. Here, we demonstrate that this process reciprocally enables formation of α-helical structure in precisely the same region formerly functioning to facilitate β-strand-mediated self-association. We further observe that the α-helical conformation allows interaction with a lipid-like detergent and that exposure to lipids enhances the β-to-α conformational switch. We hypothesize that regulation of this oxidative switch will prove to be important to the control of localized translation within vertebrate cells. The experimental observations reported herein were heavily reliant on studies of 1,6-hexanediol, a chemical agent that selectively dissolves labile structures formed via the self-association of protein domains of low sequence complexity. This aliphatic alcohol is shown to exert its dissociative activity primarily via hydrogen-bonding interactions with carbonyl oxygen atoms of the polypeptide backbone. Such observations underscore the central importance of backbone-mediated protein:protein interactions that facilitate the self-association and phase separation of LCDs.

Role of Charge Ordering in the Dynamics of Cluster Formation in Associated Liquids.

Liquids are archetypes of disordered systems, yet liquids of polar molecules are locally more ordered than nonpolar molecules, due to the Coulomb interaction based charge ordering phenomenon. Hydrogen bonded liquids, such as water or alcohols, for example, represent a special type of polar liquids, in that they form labile clustered local structures. For water, in particular, hydrogen bonding and the related local tetrahedrality, play an important role in the various attempts to understand this liquid. However, labile structures imply dynamics, and it is not clear how it affects the understanding of this type of liquids from purely static point of view. Herein, we propose to reconsider hydrogen bonding as a charge ordering process. This concept allows us to demonstrate the insufficiency of the analysis of the microscopic structure based solely on static pair correlation functions, and the need for dynamical correlation functions, both in real and reciprocal space. The subsequent analysis allows to recover several aspects of our understanding of hydrogen bonded liquids, but from the charge order perspective. For water, it confirms the jump rotation picture found recently, and it allows to rationalize the contradicting pictures that arise when following the interpretations based on hydrogen bonding. For alcohols, it allows to understand the dynamical origin of the scattering prepeak, which does not exist for water, despite the fact that both these liquids have very similar hydroxyl group chain clusters. The concept of charge ordering complemented by the analysis of dynamical correlation functions appear as a promising way to understand microheterogeneity in complex liquids and mixtures from kinetics point of view.

A STATISTICAL META-ANALYSIS OF LITHOLOGIC AND OTHER POTENTIAL CONTROLS ON FOSSIL BONE CELLULAR AND SOFT TISSUE PRESERVATION

ABSTRACT Demineralization assays, utilizing weak acids to isolate organics from biomineralized tissues, have recently been applied with increasing frequency to explore soft tissue preservation in fossils, revealing frequent retention of cells and other pliable microstructures in fossil bones. However, factors controlling long-term preservation of such labile structures remain mysterious. To address this, we compiled a database of bone demineralization results from 29 studies, then conducted a statistical meta-analysis of these data to evaluate the importance of specimen age, taxonomy, entombing lithology, and bone tissue type on microstructure recovery. Our database encompasses results from 137 bones from 44 formations spanning the Permian to the Holocene. Osteocytes, blood vessels, and fibrous/proteinaceous matrix each exhibit bimodal recovery patterns in which most fossil bones either yield many or none of these microstructures. Though their relative abundances in any given fossil bone are extremely variable, statistically significant Fisher's Exact tests found that if a bone yields one of these types of microstructures in abundance then the others are usually also abundant. None of the variables examined significantly influence osteocyte recovery, but Kruskal-Wallis and subsequent pairwise Mann-Whitney tests revealed that bones collected from unconsolidated sediments, of Paleocene age, and/or deriving from birds, amphibians, marine reptiles, or crocodylians often yield few or no vessels and fibrous matrix. Although these findings hint at possible controls on cellular and soft tissue preservation in fossil bones, they should be viewed cautiously as they are demonstrably biased by uneven sampling. For example, many of the apparent trends are substantially controlled by overrepresentation of data from nonavian dinosaur specimens from Cretaceous fluvio-lacustrine deposits. Future demineralization assays should therefore focus on non-mammalian specimens from the Cenozoic and Jurassic-and-older nondinosaurian specimens, especially those preserved in less-common depositional environments (e.g., eolian settings).

Characterizing Non-covalent Protein Complexes Using Asymmetrical Flow Field-Flow Fractionation On-Line Coupled to Native Mass Spectrometry

We report an online analytical platform based on the coupling of asymmetrical flow field-flow fractionation (AF4) and native mass spectrometry (nMS) in parallel with UV-absorbance, multi-angle light scattering (MALS), and differential-refractive-index (UV-MALS-dRI) detectors to elucidate labile higher-order structures (HOS) of protein biotherapeutics. The technical aspects of coupling AF4 with nMS and the UV-MALS-dRI multi-detection system are discussed. The "slot-outlet" technique was used to reduce sample dilution and split the AF4 effluent between the MS and UV-MALS-dRI detectors. The stability, HOS, and dissociation pathways of the tetrameric biotherapeutic enzyme (anticancer agent) l-asparaginase (ASNase) were studied. ASNase is a 140 kDa homo-tetramer, but the presence of intact octamers and degradation products with lower molecular weights was indicated by AF4-MALS/nMS. Exposing ASNase to 10 mM NaOH disturbed the equilibrium between the different non-covalent species and led to HOS dissociation. Correlation of the information obtained by AF4-MALS (liquid phase) and AF4-nMS (gas phase) revealed the formation of monomeric, tetrameric, and pentameric species. High-resolution MS revealed deamidation of the main intact tetramer upon exposure of ASNase to high pH (NaOH and ammonium bicarbonate). The particular information retrieved from ASNase with the developed platform in a single run demonstrates that the newly developed platform can be highly useful for aggregation and stability studies of protein biopharmaceuticals.

Strong Ferromagnetic Manipulation of SrTiO3 from CO2 -Straining Effect on Electronic Structure Modulation.

2D magnetic materials are ideal to fabricate magneto-optical, magneto-electric, and data storage devices, which are proposed to be critical to the next generation of information technologies. Benefited from their labile structures, 2D perovskites are amenable for magnetic manipulation through structural optimization. In this work, 2D room-temperature ferromagnetic SrTiO3 is achieved through straining effect induced by supercritical carbon dioxide (SC CO2 ). According to experimental results, the cubic phase of SrTiO3 is converted to tetragonal with exposure of (110), (200), (111), and (211) planes over the SC CO2 treatment, leading to significant ferromagnetic enhancement. Theoretical calculations illustrate that over the conversion from cubic to tetragonal, the electronic structure of SrTiO3 is significantly modulated. Specifically, the spin density of planes of (200), (111), and (211) is enhanced, presumably due to the stabilization of the highest occupied molecular orbital over straining by SC CO2 , leading to magnetic optimizations. This work suggests that magnetic optimization can be achieved from SC CO2 -induced electronic structure modulation.

Molecular Scale Structure and Kinetics of Layer-by-Layer Peptide Self-Organization at Atomically Flat Solid Surfaces.

Understanding the mechanisms of self-organization of short peptides into two- and three-dimensional architectures are of great interest in the formation of crystalline biomolecular systems and their practical applications. Since the assembly is a dynamic process, the study of structural development is challenging at the submolecular dimensions continuously across an adequate time scale in the natural biological environment, in addition to the complexities stemming from the labile molecular structures of short peptides. Self-organization of solid binding peptides on surfaces offers prospects to overcome these challenges. Here we use a graphite binding dodecapeptide, GrBP5, and record its self-organization process of the first two layers on highly oriented pyrolytic graphite surface in an aqueous solution by using frequency modulation atomic force microscopy in situ. The observations suggest that the first layer forms homogeneously, generating self-organized crystals with a lattice structure in contact with the underlying graphite. The second layer formation is mostly heterogeneous, triggered by the crystalline defects on the first layer, growing row-by-row establishing nominally diverse biomolecular self-organized structures with transient crystalline phases. The assembly is highly dependent on the peptide concentration, with the nucleation being high in high molecular concentrations, e.g., >100 μM, while the domain size is small, with an increase in the growth rate that gradually slows down. Self-assembled peptide crystals are composed of either singlets or doublets establishing P1 and P2 oblique lattices, respectively, each commensurate with the underlying graphite lattice with chiral crystal relations. This work provides insights into the surface behavior of short peptides on solids and offers quantitative guidance toward elucidating molecular mechanisms of self-assembly helping in the scientific understanding and construction of coherent bio/nano hybrid interfaces.

Вплив вод морського і континентального походження на процеси трансформації глинистих мінералів евапоритових відкладів (на прикладі Калуш-Голинського родовища Передкарпатського прогину)

The influence of the chemical composition of marine and continental waters on the formation and transformation of clay minerals is considered on the example of evaporites of the Kalush-Holin’ potash deposit of the Carpathian Foredeep. Clay minerals under variable physical and chemical conditions become unstable and transformed, adapting to new conditions. The main factor that causes changes in their composition and structure is the concentration of brines. The increased concentration of brines at the stage of deposition of potassium salts contributed to the aggradational transformation of clay minerals, the transformation of labile minerals into illite and chlorite that are stable in the hipersaline environment. These two minerals – illite and chlorite are characteristic of the Kalush-Holin’ potash deposit. Further arrangement of the structure leads to the transformation of part of the illite into mica. On the clay fraction diffractograms of some potash rocks, the basal reflex 001 is wide and bifurcated at the top on a line with interplanar distances of 0.99 and 1.0 nm, this indicates the presence of structurally similar minerals – mica and illite. Under conditions of hypergenesis, when evaporite deposits are washed away by fresh surface waters, a reverse process (degradational transformation) takes place, which occurs in the leaching of potassium from the interlayer space of a part of illite and the formation of labile clay structures. The clay mineral association of the gypsum-clay caprock of evaporite deposits, in addition to illite and chlorite, also contains mixed-layer illite-smectite and kaolinite – the appearance of these clay minerals in hypergenic deposits is the result of degradational transformation (illite-smectite) and formation de novo (kaolinite) under conditions of decreased saline brine concentration. Capture of potassium by the structure of the mixed-layer illite-smectite and its transition into illite (aggradational transformation) occurs more easily than the reverse process – potassium leaching and transformation of illite into a mixed-layer illite-smectite (degradational transformation).

PolyQ-Expanded Mutant Huntingtin Forms Inclusion Body Following Transient Cold Shock in a Two-Step Aggregation Mechanism.

Age-dependent formation of insoluble protein aggregates is a hallmark of many neurodegenerative diseases. We are interested in the cell chemistry that drives the aggregation of polyQ-expanded mutant Huntingtin (mHtt) protein into insoluble inclusion bodies (IBs). Using an inducible cell model of Huntington's disease, we show that a transient cold shock (CS) at 4 °C followed by recovery incubation at temperatures of 25-37 °C strongly and rapidly induces the compaction of diffuse polyQ-expanded HuntingtinExon1-enhanced green fluorescent protein chimera protein (mHtt) into round, micron size, cytosolic IBs. This transient CS-induced mHtt IB formation is independent of microtubule integrity or de novo protein synthesis. The addition of millimolar concentrations of sodium chloride accelerates, whereas urea suppresses this transient CS-induced mHtt IB formation. These results suggest that the low temperature of CS constrains the conformation dynamics of the intrinsically disordered mHtt into labile intermediate structures to facilitate de-solvation and hydrophobic interaction for IB formation at the higher recovery temperature. This work, along with our previous observation of the effects of heat shock protein chaperones and osmolytes in driving mHtt IB formation, underscores the primacy of mHtt structuring and rigidification for H-bond-mediated cross-linking in a two-step mechanism of mHtt IB formation in living cells.

The contributions of soil biochemical characteristics and soil organic carbon (SOC) structure to SOC mineralization rate during forest succession on the Loess Plateau, China

AbstractSoil organic carbon (SOC) mineralization is a process driven by microorganisms and is considered to be one of the main forms of carbon loss in land restoration. However, the interaction of SOC structures and bacteria that drive SOC mineralization remain unclear. Therefore, four forest succession stages were investigated on the Loess Plateau of Northern China: (1) primary stage Betula platyphylla (BP); (2) transitional stage which were two mixed communities of Populus davidiana and Quercus wutaishanica with different proportions (PQ1); (3) (PQ2) and (4) the late stage was climax communities of Quercus wutaishanica (QW). The Illumina sequencing of the 16S rRNA gene and Fourier transformation infrared (FTIR‐ATR) spectroscopy were used to clarify the regulation mechanism of microbial activity on SOC mineralization during forest succession through the perspective of SOC structures. Our results indicated higher aromatics‐C in QW contributed to decreased SOC mineralization ratio (SMR). Redundancy analysis confirmed SOC structures–bacteria interaction and revealed the groups Acidobacteria correlated with recalcitrant SOC structures while Proteobacteria and Bacteroides correlated with labile SOC structures, respectively. Moreover, the partial least squares path model revealed that the SOC and C:N ratio act on soil bacteria community characteristics, and the higher abundance of Acidobacteria and the increase of aromatics‐C decreased SMR. Collectively, these findings highlight the importance of bacteria–SOC structures interaction in decreased SMR and contribute to an improved understanding of how forest succession regulates carbon mineralization.

Enhanced calcium release at specialised surface sites compensates for reduced t-tubule density in neonatal sheep atrial myocytes

Cardiac myocytes rely on transverse (t)-tubules to facilitate a rapid rise in calcium throughout the cell. However, despite their importance in triggering synchronous Ca2+ release, t-tubules are highly labile structures. They develop postnatally, increase in density during exercise training and are lost in diseases such as heart failure (HF). In the majority of settings, an absence of t-tubules decreases function. Here we show that despite reduced t-tubule density due to immature t-tubules, the newborn atrium is highly specialised to maintain Ca2+ release. To compensate for fewer t-tubules triggering a central rise in Ca2+, Ca2+ release at sites on the cell surface is enhanced in the newborn, exceeding that at all Ca2+ release sites in the adult. Using electron and super resolution microscopy to investigate myocyte ultrastructure, we found that newborn atrial cells had enlarged surface sarcoplasmic reticulum and larger, more closely spaced surface and central ryanodine receptor clusters. We suggest that these adaptations mediate enhanced Ca2+ release at the sarcolemma and aid propagation to compensate for reduced t-tubule density in the neonatal atrium.

Spectroscopic Investigation on the Effects of Biochar and Soluble Phosphorus on Grass Clipping Vermicomposting

Seeking to evaluate the hypothesis that biochar optimises the composting and vermicomposting processes as well as their product quality, we carried out field and greenhouse experiments. Four grass clipping composting treatments (only grass, grass + single superphosphate (SSP), grass + biochar and grass + SSP + biochar) were evaluated. At the end of the maturation period (150 days), the composts were submitted to vermicomposting (Eisenia fetida earthworm) for an additional 90 days. Ordinary fine charcoal was selected due to its low cost (a by-product of charcoal production) and great availability; this is important since the obtained product presents low commercial value. A greater maturity of the organic matter (humification) was observed in the vermicompost treatments compared with the compost-only treatments. The addition of phosphate significantly reduced the pH (from 6.7 to 4.8), doubled the electrical conductivity and inhibited biological activity, resulting in less than 2% of the number of earthworms found in the treatment without phosphate. The addition of soluble phosphate inhibited the humification process, resulting in a less-stable compound with the preservation of labile structures, primarily cellulose. The P species found corroborate these findings because the pyrophosphate conversion from SSP in the absence of biochar may explain the strong acidification and increased electric conductivity. Biochar appears to prevent this conversion, thus mitigating the deleterious effects of SSP and favouring the formation of organic P species from SSP (78.5% of P in organic form with biochar compared to only 12.8% in the treatments without biochar). In short, biochar decreases pyrophosphate formation from SSP, avoiding acidification and salinity; therefore, biochar improves the whole composting and vermicomposting process and product quality. Vermicompost with SSP and biochar should be tested as a soil conditioner on account of its greater proportion of stabilized C and organic P.

Mutations linked to neurological disease enhance self-association of low-complexity protein sequences.

Protein domains of low sequence complexity do not fold into stable, three-dimensional structures. Nevertheless, proteins with these sequences assist in many aspects of cell organization, including assembly of nuclear and cytoplasmic structures not surrounded by membranes. The dynamic nature of these cellular assemblies is caused by the ability of low-complexity domains (LCDs) to transiently self-associate through labile, cross-β structures. Mechanistic studies useful for the study of LCD self-association have evolved over the past decade in the form of simple assays of phase separation. Here, we have used such assays to demonstrate that the interactions responsible for LCD self-association can be dictated by labile protein structures poised close to equilibrium between the folded and unfolded states. Furthermore, missense mutations causing Charcot-Marie-Tooth disease, frontotemporal dementia, and Alzheimer's disease manifest their pathophysiology in vitro and in cultured cell systems by enhancing the stability of otherwise labile molecular structures formed upon LCD self-association.

Shoulderless Friction Stir Welding: a low-force solid state keyhole joining technique for deep welding of labile structures

This paper reports on the possibility of performing Friction Stir Welding (FSW) without the usual immanent shoulder to enable FS processing to deep welding of narrow and labile structures and applications where backing is not possible. Requirements and prerequisites, advantages and limitations for Shoulderless Friction Stir Welding (SLFSW) are discussed and an industrial application of the joining technology is presented. For leaving the shoulder out, its central functions in FSW have to be transferred to the pin. The resulting tool design of SLFSW is comparably small and slim and so reduces contact area and effective lever and in turn forces and heat input during processing. SLFSW allows welding paths almost at the edge of components and enables a complete and gap-free joining while a deformation of overhanging structures can be avoided. Compared to standard FSW processes, force reductions of about 80–85 % and power reductions of about 75–80 % were found in this study for a 6.5 mm deep weld opening up additional potential for integration with other spindle processes like milling. The locally very limited process impact of SLFSW resulted in comparably low distortion with a part precision reached of +/− 0.05 mm.

Gas Cell Infrared and Attenuated Total Reflection Infrared Spectroscopic Studies for Organic-Inorganic Interactions in Adsorption of Fulvic Acid on the Goethite Surface Generating Carbon Dioxide.

The generation of carbon dioxide (CO2) from Nordic fulvic acid (FA) solution in the presence of goethite (α-FeOOH) was observed in FA-goethite interaction experiments at 25-80 ℃. CO2 generation processes observed by gas cell infrared (IR) spectroscopy indicated two steps: the zeroth order slower CO2 generation from FA solution commonly occurring in the heating experiments of the FA in the presence and absence of goethite (activation energy: 16-19 kJ mol-1), and the first order faster CO2 generation from FA solution with goethite (activation energy: 14 kJ mol-1). This CO2 generation from FA is possibly related to redox reactions between FA and goethite. In situ attenuated total reflection infrared (ATR-IR) spectroscopic measurements indicated rapid increases with time in IR bands due to COOH and COO- of FA on the goethite surface. These are considered to be due to adsorption of FA on the goethite surface possibly driven by electrostatic attraction between the positively charged goethite surface and negatively charged deprotonated carboxylates (COO-) in FA. Changes in concentration of the FA adsorbed on the goethite surface were well reproduced by the second order reaction model giving an activation energy around 13 kJ mol-1. This process was faster than the CO2 generation and was not its rate-determining step. The CO2 generation from FA solution with goethite is faster than the experimental thermal decoloration of stable structures of Nordic FA in our previous report possibly due to partial degradations of redox-sensitive labile structures in FA.