Large Structural Changes Research Articles

Sexual violence affecting female sex workers in Côte d’Ivoire: prevalence, context, and associated mental health and substance use outcomes

BackgroundFemale sex workers are disproportionately affected by sexual violence, which is associated with an increased risk of poor mental health outcomes, substance use, and decreased access to health resources. Understanding the pathways through which sexual violence impacts these outcomes can inform strategies that appropriately and effectively meet the health needs of sex workers.MethodsThis study investigated the prevalence of sexual violence among female sex workers in Côte d’Ivoire, and the relationship between sexual violence and adverse mental health and substance use outcomes. We examined survey data from female sex workers recruited between November 2019 and May 2020 across five regions of Côte d’Ivoire using respondent driven sampling (RDS), as part of an integrated bio-behavioral survey. The primary exposure of interest was self-reported lifetime experience of sexual violence, and the main outcomes of interest included depression, suicidal ideation, counselling seeking, alcohol consumption, and substance use. Multivariable logistic regression models investigated associations between exposure to sexual violence and the key mental health and substance use outcomes of interest. For each outcome, a directed acyclic graph was developed to identify a minimally sufficient set of covariates for adjustment. Additional sociodemographic characteristics, experiences, and sex work-related behaviors were explored in descriptive analyses using crude and RDS adjusted estimates.ResultsOut of 1,177 participants, 376 (31.9%; RDS weighted: 30.5%; 95% CI: 24.7, 36.3) reported having experienced sexual violence in their lifetime, and of those 31.9% (RDS weighted: 31.2%; 95% CI: 21.3, 41.1) had experienced sexual violence within the previous 12 months. Experience of sexual violence was associated with an increased odds of suicidal ideation (aOR: 1.95; 95% CI: 1.48, 2.55), illicit drug use in the last 12 months (aOR: 2.40; 95% CI: 1.50, 3.86), daily alcohol use (aOR: 1.63; 95% CI: 0.99, 2.67), and having spoken to a counselor or confidant (aOR: 1.90; 95% CI: 1.34, 2.68).ConclusionFindings confirm a high burden of sexual violence among female sex workers in Côte d’Ivoire, and a need to implement large structural changes that enable female sex workers to seek protection as well as health resources after experiencing sexual violence. This may include reform in the form of targeted social, clinical and mental health resources, along with community development opportunities.

Fast diffusion and stable topotactic reaction in single crystal conversion anode

Conversion electrodes typically have high theoretical specific capacity, but mostly suffer large structural changes during charge/discharge and result in poor cycling stability. The optimization of the polycrystalline materials is the mostly used strategy, however, these polycrystalline materials are intrinsically vulnerable to grain-boundary (intergranular) fracture caused by the anisotropic volume change during sodiation/desodiation, resulting in rapid impedance growth and capacity decay. Herein, we propose an alternative pathway to design single-crystal materials as potential conversion anodes. As an example, SnO2 with different crystallinities is successfully synthesized via solvothermal methods and compared to determine the implications of different crystallinity for the electrochemical properties of conversion anodes. It is demonstrated that the single-crystal SnO2 not only has faster Na+ diffusion dynamics but also maintains structural stability via topotactic reaction. Further optimization of the electron conduction and structural robustness is realized by uniformly covering a graphitic carbon shell on the surface of single-crystal SnO2 nanosheets. The modified single-crystal SnO2 exhibits a high reversible capacity of 436.2 mA h g–1 and maintains a high capacity of 257.1 mA h g-1 and remarkable capacity retention of about 98.9% after 9000 cycles at 5000 mA g-1. The deep understandings of the topotactic reaction in single crystal conversion anode in this work provide a theoretical foundation and new direction for further developing electrode materials with excellent electrochemical performance, especially high rate capabilities, and long cyclability.

Genotype–phenotype findings in patients with mucopolysaccharidosis II from the Hunter Outcome Survey

PurposeThis study investigated the relationship between mucopolysaccharidosis II (MPS II) iduronate-2-sulfatase gene (IDS) variants and phenotypic characteristics, particularly cognitive impairment, using data from the Hunter Outcome Survey (HOS) registry. MethodsHOS data for male patients (n = 650) aged ≥5 years at latest cognitive assessment with available genetic data were analyzed. Predefined genotype categories were used to classify IDS variants and report phenotypic characteristics by genotype. ResultsAt their latest cognitive assessment, 411 (63.2%) of 650 patients had cognitive impairment. Missense variants were the most common MPS II genotype, with about equal frequency for patients with and patients without cognitive impairment. Complete deletions/large rearrangements were associated with cognitive impairment. Cognitive impairment and behavioral issues were most common, and height and weight abnormalities most apparent, in patients with large IDS structural changes. Broadly, missense variants NM-000202.8:c.998C>T p.(Ser333Leu), NM-000202.8:c.1402C>T p.(Arg468Trp), NM-000202.8:c.1403G>A p.(Arg468Gln) and NM-000202.8:c.262C>T p.(Arg88Cys), and splice site variant NM-000202.8:c.257C>T p.(Pro86Leu), were associated with cognitive impairment, and variants NM-000202.8:c.253G>A p.(Ala85Thr), NM-000202.8:c.187 A>G p.(Asn63Asp), NM-000202.8:c.1037C>T p.(Ala346Val), NM-000202.8:c.182C>T p.(Ser61Phe) and NM-000202.8:c.1122C>T were not. ConclusionThis analysis contributes toward the understanding of MPS II genotype–phenotype relationships, confirming and expanding on existing findings in a large, geographically diverse population.

An insight into structure-activity relationships in subclass IIb bacteriocins: Plantaricin EvF

This study reports the structure-activity relationships of a unique subclass IIb bacteriocin, plantaricin EvF, which consists of two peptide chains and possesses potent antimicrobial activity. Because the plantaricin Ev peptide chain lacks an α-helix structure, plantaricin EvF is unable to exert its antimicrobial activity through helix-helix interactions like typical subclass IIb bacteriocins. We have shown by various structural evaluation methods that plantaricin Ev can be stabilized by hydrogen bonding at amino acid residues R3, V12, and R13 to the N-terminal region of plantaricin F. This binding gives plantaricin EvF a special spade-shaped structure that exerts antimicrobial activity. In addition, the root-mean-square deviations (RMSDs) of the amino acid residues Y6, F8, and R13 of plantaricin Ev pre- and post-binding were 1.512, 1.723, and 1.369, respectively, indicating that they underwent large structural changes. The alanine scanning experiments demonstrated the important role of the above key amino acids in maintaining the structural integrity of plantaricin EvF. This study not only reveals the unique structural features of plantaricin EvF, but also provides an insight into the structure-activity relationships of subclass IIb bacteriocins.

Tailoring body center tetragonal allotropes Cx (x = 8, 12, 16, 20) with C(sp3) and hybrid C(sp3)/C(sp2): Crystal chemistry and ab initio investigations of the physical properties

Based on literature tetragonal ths topology C8 characterized by trigonal C(sp2), selective insertions of carbon induce large structural changes leading to C(sp3) C12 with dia topology after geometry optimizations to ground state structure using calculations within the quantum density functional theory DFT. Further crystal engineering operated on C12 lead to complete the series with novel C16 and C20. Such allotropes respectively characterized by ene (C=C) and propadiene (C=C=C) -like units beside C4 tetrahedra reveal hybrid C(sp3)/C(sp2) with complex stc topology. Alike ths C8, all three allotropes (C12, C16, and C20) identified in high symmetry I41/amd (No. 141) space group are cohesive with larger magnitude for C12 than for ths C8 and close energies for C16 and C20. Mechanical properties show diamond-like Vickers hardness HV for C12 (HV = 95 GPa) and smaller magnitudes for mixed C(sp3)/C(sp2) C16 (HV = 26 GPa) and C20 (HV = 47 GPa), noting that C8 with C(sp2) was found with the largest compressibility with HV = 19 GPa. Dynamically, all allotropes are stable from positive phonon acoustic and optic frequencies with the largest frequency magnitudes for C16 and C20 corresponding to CC and C=C=C vibrations respectively. Thermodynamically, the temperature changes of the specific heat CV show close agreement with diamond experimental values for C12 and larger magnitudes for the three other allotropes. Electronic band structure analyses reveal conductive C8 and C16, insulating C12 with a large band gap close to diamond's and semi-conducting C20 with small band gap.

In-situ synthesis of Fe3O4@Fe3C nanoparticles with heterostructures embedded in the N-doped porous carbon for high-performance lithium ion batteries

Metal oxides (Fe3O4) have attracted immense attention as high-capacity anode materials for high-performance electrochemical energy storage systems. However, the large structural change and sluggish reaction kinetics in the lithiation and delithiation reactions critically limit their practical development. Here, we design a novel composite consisting of Fe3O4@Fe3C nanoparticles embedded in N-doped porous carbon (Fe3O4@Fe3C-NPC) for lithium ion batteries. Benefiting from the synergistic effect of heterostructures, the Fe3O4@Fe3C-NPC delivers high reversible capacities (911.9 mAh g−1 at 0.2 A g−1, 319.6 mAh g−1 at 5.0 A g−1). The formed heterointerfaces can build an internal electric field, which help to improve reaction kinetics with fast ion diffusion kinetics and low charge transfer resistance. Furthermore, the Fe3O4@Fe3C-NPC//LiFePO4 full cell also displays great performance. The structural design concept and efficient synthesis method in the work can be extended to construct metal oxide/carbide heterostructures for anode materials.

From 2D to 3D: WS2/MoS2 heterostructure in-situ anchored on Ti3C2Tx MXene with enhanced ion/electron migration and sodium storage at −20 ℃

Layered transition metal dichalcogenides (TMDs), featuring robust electrochemical activity, high capacity, and large interlayer spacing, have attracted widespread interest in research on sodium storage. However, the limitations in dynamics and structure expansion lead to degraded cycling life and rate capability, especially in cold climate with low temperatures. Generally, heterostructure engineering, combined with conductive matrix, gives a promise towards enhancing electronic transportation, accelerating ionic diffusion, and alleviating large structure change of layered TMDs upon sodium storage. Herein, a robust WS2/MoS2 heterostructure, rendering ultrafast charge transfer, is presented, and further hybridization with layered conductive Ti3C2Tx MXene results in three-dimensional crosslinked nanoarchitectonics, leading to electrochemical performance at 25 °C and -20 °C, which shows only 0.03 % capacity degradation per cycle up to 2800 cycles at 2.0 A g−1 (25 °C). Strikingly, the desired WS2/MoS2/Ti3C2Tx exhibits a high capacity of 293.7 mAh g−1 (100 cycles) at 0.1 A g−1 even at −20 °C. Besides, density functional theory calculations further manifest the decreased sodium diffusion barrier and facilitated charge-transfer dynamics in the designed heterostructure with Ti3C2Tx. More importantly, this work not only represents the correlation between structure and performance for target electrode, but also provides a deep insight for the rational design of heterostructure/Ti3C2Tx MXene for next-generation high-performance electrode materials.

Logging response alters trajectories of reorganization after loss of a foundation tree species.

Forest insect outbreaks cause large changes in ecosystem structure, composition, and function. Humans often respond to insect outbreaks by conducting salvage logging, which can amplify the immediate effects, but it is unclear whether logging will result in lasting differences in forest structure and dynamics when compared with forests affected only by insect outbreaks. We used 15 years of data from an experimental removal of Tsuga canadensis (L.) Carr. (Eastern hemlock), a foundation tree species within eastern North American forests, and contrasted the rate, magnitude, and persistence of response trajectories between girdling (emulating mortality from insect outbreak) and timber harvest treatments. Girdling and logging were equally likely to lead to large changes in forest structure and dynamics, but logging resulted in faster rates of change. Understory light increases and community composition changes were larger and more rapid in the logged plots. Tree seedling and understory vegetation abundance increased more in the girdled plots; this likely occurred because seedlings grew rapidly into the sapling- and tree-size classes after logging and quickly shaded out plants on the forest floor. Downed deadwood pools increased more after logging but standing deadwood pools increased dramatically after girdling. Understory light levels remained elevated for a longer time after girdling. Perhaps because the window of opportunity for understory species to establish was longer in the girdled plots, total species richness increased more in the girdled than logged plots. Despite the potential for greater diversity in the girdled plots, Betula lenta L. (black birch) was the most abundant tree species recruited into the sapling- and tree-size classes in both the girdled and logged plots and is poised to dominate the new forest canopy. The largest difference between the girdling and logging treatments-deadwood structure and quantity-will persist and continue to bolster aboveground carbon storage and structural and habitat diversity in the girdled plots. Human responses to insect outbreaks hasten forest reorganization and remove structural resources that may further alter forest response to ongoing climate stress and future disturbances.

Re-assessment of a blackfoot abalone (Haliotis iris) population in Peraki Bay, New Zealand, after 45 years

ABSTRACT Marine species are facing an increasing number of stressors and some species once thought to be resilient to change are now threatened. It is important to understand how species populations have changed through time so that management can be adjusted accordingly, and so that achievable restoration goals can be set. However, many species lack population data at multidecadal or longer time scales. Using historical data from the 1970s, this study investigates how the dynamics of a New Zealand abalone (Haliotis iris), or pāua, population at Peraki Bay changed over a 45-year period. No commercial fishing of the population occurred prior to the initial survey and limited commercial catch has been reported between surveys. Repeat monitoring of the H. iris population at a 45-year interval indicates that a large change in population size and structure had occurred. Since 1976, there has been an 84% decrease in estimated population size. The remaining population is restricted to where juveniles were found in the original survey. These findings are consistent with conclusions, made from modelling in the 1970s, that the population seen in the 1970s was not stable and that a possible cause was temporal variability in population recruitment.

Attachment of Proteolytic Enzyme Inhibitors to Vascular Prosthesis-An Analysis of Binding and Antimicrobial Properties.

Prosthetic infections are associated with high morbidity, mortality, and relapse rates, making them still a serious problem for implantology. Staphylococcus aureus is one of the most common bacterial pathogens causing prosthetic infections. In response to the increasing rate of bacterial resistance to commonly used antibiotics, this work proposes a method for combating pathogenic microorganisms by modifying the surfaces of synthetic polymeric biomaterials using proteolytic enzyme inhibitors (serine protease inhibitors-4-(2-aminoethyl)benzenesulfonyl fluoride hydrochloride and puromycin). While using techniques based on the immobilization of biologically active molecules, it is important to monitor the changes occurring on the surface of the modified biomaterial, where spectroscopic techniques (e.g., FTIR) are ideal. ATR-FTIR measurements demonstrated that the immobilization of both inhibitors caused large structural changes on the surface of the tested vascular prostheses (polyester or polytetrafluoroethylene) and showed that they were covalently bonded to the surfaces of the biomaterials. Next, the bactericidal and antibiofilm activities of the tested serine protease inhibitors were determined using the CLSM microscopic technique with fluorescent staining. During LIVE/DEAD analyses, a significant decrease in the formation of Staphylococcus aureus biofilm after exposure to selected concentrations of native inhibitors (0.02-0.06 mg/mL for puromycin and 0.2-1 mg/mL for 4-(2-aminoethyl)benzenesulfonyl fluoride hydrochloride) was demonstrated.

Adaption planning to climate change in industrial fisheries: Progress in the Basque tropical tuna fishery

Climate change impacts on ocean living organisms and ecosystems have flow-on effects on fisheries and their associated values. Industrial fisheries operate long distance fleets that potentially have the capacity to respond to such impacts by using technology and changing the timing and distribution of fishing effort. However, long-term adaptation to climate change in industrial fisheries entails larger structural changes that include adaptive management and international cooperation, where actors beyond the industry need to be engaged. How industrial fisheries are tackling adaptation to climate change is largely unknown, as is the role that actors in these systems undertake. In this study, we explored the Basque tropical tuna fishery to understand past and projected adaptation actions by each of the main actors in the fishery. We performed in-depth interviews with high-level representatives from 65% of the fishing industry, governments, research bodies, and non-governmental organizations of the Basque tropical tuna freezer purse seine fishery operating in the central-eastern Atlantic Ocean. We found that the fishery system has engaged in adaptation actions that seek to improve fishery sustainability, and that most adaptation actions are undertaken by the fishing industry. We also found that actors promote several types of adaptation actions such as practice change, and capacity building, among others, and that there is a lack of joint adaptation planning. We discuss the challenge in identifying suitable adaptation options to promote resilient and sustainable fisheries and to avoid losing their associated values.

A high-performance C@Na5V12O32 nanowire electrode derived from the reconstruction of carbon quantum dots.

Vanadate electrodes are potential candidates for lithium-ion batteries (LIBs) due to their large theoretical specific capacity. However, their easy dissolution in the electrolyte, large structural changes, low conductivity and capacity decay during cycling hinder their further application. Herein, a lithium-ion battery electrode of Na5V12O32 (NVO) nanowires covered with a carbon film and formed by the reconstruction of carbon quantum dots (CDs) was obtained using an in situ capping strategy. Remarkably, the carbon film could prevent direct contact between the NVO nanowires and the electrolyte, thus slowing down the occurrence of side reactions and avoiding the dissolution of the NVO nanowires. Among the electrodes treated at different temperatures, the C@NVO-400 electrode exhibits high capacity and excellent cycling stability as the electrode of LIBs, with a discharge specific capacity of 779.1 and 315.5 mAh g-1 after 400 and 1000 cycles at a current density of 0.1 and 2 A g-1, respectively. An in situ coating strategy is proposed here to contribute to the further development of coated vanadate electrodes for high-performance LIBs.

Spectroscopic and thermodynamic characterization of a cobalt-verdazyl valence tautomeric system. influence of crystal structure, solvent and counterion.

Crystallization of the verdazyl-based valence tautomeric ion [Co(dipyvd)2]2+ (where dipyvd is the radical ligand 1-isopropyl-3,5-di(2'-pyridyl)-6-oxoverdazyl) with a variety of different counterions results in materials that show varying degrees of valence tautomeric (VT) transition in the solid state. The X-ray structure of the SbF6 salt at 150 K reveals a localized structure for the S = 1/2 tautomer, with a Co3+ cation and distinct anionic and radical ligands. Comparison with the structure of the same material at 300 K reveals large structural changes in the ligand as a result of the valence tautomeric equilibrium. Data for the S = 3/2 form is less conclusive; X-ray spectroscopy on the PF6 salt suggests a degree of low spin Co2+ character for the S = 3/2 tautomer at very low temperature though this is inconsistent with EPR data at similar temperatures and structural information at 150 K. Magnetic measurements on the [BArF4]- and triflate salts in organic solvents show that the VT equilibrium is dependent on solvent and ion pairing effects.

The AM-4 Family of Layered Titanosilicates: Single-Crystal-to-Single-Crystal Transformation, Synthesis and Ionic Conductivity.

Flexible crystal() structures, which exhibit() single-crystal()-to-single-crystal() (SCSC) transformations(), are attracting attention() in many applied aspects: magnetic() switches, catalysis, ferroelectrics and sorption. Acid treatment() for titanosilicate material() AM-4 and natural() compounds with the same structures led to SCSC transformation() by loss() Na+, Li+ and Zn2+ cations with large structural() changes (20% of the unit()-cell() volume()). The conservation() of crystallinity through complex() transformation() is possible due() to the formation() of a strong hydrogen bonding() system(). The mechanism() of transformation() has been characterized using single-crystal() X-ray() diffraction analysis(), powder() diffraction, Rietvield refinement, Raman spectroscopy and electron microscopy. The low migration() energy() of cations in the considered materials() is confirmed using bond()-valence and density() functional() theory() calculations, and the ion conductivity of the AM-4 family's materials() has been experimentally verified.

Investigation of Stable Structures and Electronic States of Spinel MgCo2−ZNi0.5MnAlzO4 (z = 0, 0.3) during Discharge Process As Cathode Materials for Magnesium Rechargeable Batteries Using First-Principles Calculations

Introduction Recently, it is focused on storage batteries materials for reduce of greenhouse gases. In particular, the development of large equipment like as electric vehicles is driving demand for storage battery materials. Although lithium-ion batteries are currently used as storage battery devices, Li metal is a rare metal and expensive, and the development of higher capacity battery materials is needed. Our research group is focusing on magnesium secondary battery cathode materials. In previous report, spinel MgCo2-xMnxO4 (x=0~0.5) (space group Fd-3m) has synthesized and evaluated its battery characteristics, showing an initial discharge capacity of more than 200mAh/g when the Mn substitution amount is x=0.5.1) Since the inclusion of substituted species improves battery properties, we synthesized Al substituted spinel MgCo2-zNi0.5MnAlzO4. In this study, we reported that Mg/Co cation mixing, which was particularly problematic at z=0.3 was reduced compared to MgCo2-xMnxO4 resulting in improved cycle properties.2) The purpose of this study is to clarify the stable local structure of pristine and discharge process of spinel type MgCo2-zNi0.5MnAlzO4 (z=0, 0.3) and to determine the contribution of Al substitution to the electronic structure by performing electron density calculation. Calculation The structural relaxation calculation was performed by generalized gradient approximation (GGA) exchange-correlation potential used with a plane-wave cutoff energy of 550 eV, and 1×2×2 k-point mesh was applied, corresponding to the inverses of the lattice constants on Vienna Ab-initio Simulation Package (VASP) code. The convergence criterion for structural optimization was that the energy difference per iteration be less than or equal to 0.02 eV/Å. 2×1×1 supercell was created and structural relaxation calculation was performed on various initial structural models to determine the energetically optimal structure. Initial structure models were constructed to ensure reproduction of the occupancies determined by an average structure analysis from Rietveld analysis using synchrotron X-ray diffraction. Result and discussion In this study, we performed structural relaxation calculations for spinel-type MgCo2-zNi0.5MnAlzO4 (z=0, 0.3) to obtain the stable structure before and during charge-discharge. The initial model before charging and discharging was created based on the occupancy of each site obtained by crystal structure analysis using neutron diffraction measurements.2) The initial model at discharge was obtained by inserting Mg into the 16c vacancy site in the stable structure before charging and discharging. Figure 1 shows the stable structure after structural relaxation calculations before for a-1) z=0 and b-1) z=0.3 and after discharge (y=0.375) for a-2) z=0 and b-2) z=0.3, respectively. The solid circled Mg is the inserted one, and the dotted circle is the 8a site that became vacant after the structural relaxation calculation in Fig. 1. The crystal structure in pristine was spinel structure, however, it is found that the 4-coordinated 8a site became a vacancy and Mg occupied the 16c site, changing the crystal structure to a rocksalt structure after discharge. Since the 8a and 16c site are close to each other, the insertion of Mg into the 16c site causes a structural change due to the repulsion between atoms and cations on the 8a site, which leads to a chain transfer to other vacancy 16c sites. In particular, models with large structural changes tended to have stable structures. It is also found that Mg remained at the 8a site in z=0.3 shown in b-2) than in z=0 shown in a-2), and that Co at the 8a site could not move to the vacancy in z=0, and that the amount of change in the entire structure is less than that in z=0.3. As a result of partial density of states (PDOS) calculation, it is confirmed that Co and Mn had 2.6 ~ 2 valence and Mn is considerably close to 3 valence during discharge. It is also found that the PDOS of Ni did not almost change before and after discharging, and that no valence change occurred. These results are consistent with those of previously reported XANES measurements.2) Therefore, the model in Fig. 1 determined in this study is considered to be valid. Acknowledgement This research was financially supported by JST, ALCA-SPRING Grant Number JPMJAC1301, Japan. This work was also supported in part by JSPS KAKENHI Grant Number 20K15382, Japan. Dr. Koji Ohara of JASRI (Japan Synchrotron Radiation Research Institute for assistance with synchrotron X-ray total scattering measurements (BL04B2, SPring-8, Proposal Nos. 2019B1249).1) Y. Idemoto, M. Ichiyama et al., J. Power Sources, 482 , 228920 1-9 (2021)2) Y. Hirata, Y. Idemoto et al., ECS Meeting s, MA2020-02 , 3451 (2020) Figure 1

Deciphering the glass-forming ability of Al2O3-Y2O3 system from temperature susceptibility of melt structure

Despite its significance in both fundamental science and industrial applications, the glass-forming transition in the Al2O3-Y2O3 (AY) refractory system is not yet fully understood due to the elusive structure evolution upon cooling. Here, atomic-scale structural changes in AY-bearing melts with different compositions and temperatures are tracked by employing in situ high-energy synchrotron X-ray diffraction and empirical potential structure refinement simulation. We find that the glass-forming abilities (GFA) of AY-bearing melts are intriguingly correlated with the dependence of melt structure on temperature. In the case of the Al2O3 and Y3Al5O12 (YAG), the observed large structural changes from superheating to undercooling melt (i.e., higher temperature susceptibility) correspond to a low GFA. Conversely, the 74Al2O3–26Y2O3 (AY26) melt, with the smallest temperature susceptibility, exhibits the highest GFA. Simulation models illustrate that the temperature susceptibility of melt is associated with its atomic arrangement, especially the stability of cation-cation pairs. A balanced network (in AY26 melt), where the unsteady OAl3 tri-clusters are minimized and steady apex-to-apex connections between adjacent network units are abundant, contributes to stabilizing cationic interactions. This, in turn, fosters the formation of large-sized Al-O-Al rings, which topologically facilitates the subsequent glass-forming transition. Our findings provide new structural insight into the GFA of AY-bearing melts and may expand to other unconventional glass-forming systems to accelerate glassy materials design.

Restraining Quiescence Release-Related Ageing in Plant Cells: A Case Study in Carrot.

The blackening of cut carrots causes substantial economic losses to the food industry. Blackening was not observed in carrots that had been stored underground for less than a year, but the susceptibility to blackening increased with the age of the carrots that were stored underground for longer periods. Samples of black, border, and orange tissues from processed carrot batons and slices, prepared under industry standard conditions, were analyzed to identify the molecular and metabolic mechanisms underpinning processing-induced blackening. The black tissues showed substantial molecular and metabolic rewiring and large changes in the cell wall structure, with a decreased abundance of xyloglucan, pectins (homogalacturonan, rhamnogalacturonan-I, galactan and arabinan), and higher levels of lignin and other phenolic compounds when compared to orange tissues. Metabolite profiling analysis showed that there was a major shift from primary to secondary metabolism in the black tissues, which were depleted in sugars, amino acids, and tricarboxylic acid (TCA) cycle intermediates but were rich in phenolic compounds. These findings suggest that processing triggers a release from quiescence. Transcripts encoding proteins associated with secondary metabolism were less abundant in the black tissues, but there were no increases in transcripts associated with oxidative stress responses, programmed cell death, or senescence. We conclude that restraining quiescence release alters cell wall metabolism and composition, particularly regarding pectin composition, in a manner that increases susceptibility to blackening upon processing.

Mechanism of a high free-energy transduction efficiency of Bacillus PS3 F1-ATPase from the perspective of solvent entropy

Bacillus PS3 F1-ATPase is a rotary molecular motor with a 100% free-energy transduction efficiency (The 100% efficiency means that the free-energy change upon hydrolysis of adenosine triphosphate (ATP) is almost completely consumed by the external dissipation arising from the rotation of the central stalk (γ subunit) of F1-ATPase.). In this work, to elucidate the mechanism of 100% free-energy transduction efficiency, the rotation of Bacillus PS3 F1-ATPase was investigated from the perspective of solvent entropy. The two F1-ATPase structures of the catalytic- and binding-dwell states recently published were used to compute the solvation entropy (The γ subunit of the F1-ATPase structure at the binding-dwell state is rotated by 44° relative to the structure of the catalytic-dwell state). To compute the solvation entropy, the integral equation theory was used. It was found that the change in the solvent entropy of the F1-ATPase upon 44° rotation of the γ subunit is approximately zero, which is surprising because a large structural change occurs in F1-ATPase upon rotation. The present result indicated the compensation of solvent entropy in the F1-ATPase. The compensation behavior was discussed by decomposing the solvent entropy of F1-ATPase into the components of the solvent entropy of subunits and that at the interfaces between the adjacent subunits. We also discussed that the system energy and conformational entropy would also remain unchanged upon the 44° rotation of the γ subunit. Based on the results and discussion, the following rotation mechanism was proposed: the free energy of Bacillus PS3 F1-ATPase is unchanged upon rotation; and the ATP binding, hydrolysis of ATP, and release of products lead to the rotation. This mechanism is consistent with the 100% free-energy transduction efficiency of F1-ATPase.

Exploring Photoswitchable Binding Interactions with Small-Molecule- and Peptide-Based Inhibitors of Trypsin.

The ability to photochemically activate a drug, both when and where needed, requires optimisation of the difference in biological activity between each isomeric state. As a step to this goal, we report small-molecule- and peptide-based inhibitors of the same protease-trypsin-to better understand how photoswitchable drugs interact with their biological target. The best peptidic inhibitor displayed a more than fivefold difference in inhibitory activity between isomeric states, whereas the best small-molecule inhibitor only showed a 3.4-fold difference. Docking and molecular modelling suggest this result is due to a large change in 3D structure in the key binding residues of the peptidic inhibitor upon isomerisation; this is not observed for the small-molecule inhibitor. Hence, we demonstrate that significant structural changes in critical binding motifs upon irradiation are essential for maximising the difference in biological activity between isomeric states. This is an important consideration in the design of future photoswitchable drugs for clinical applications.

Nutrient-cycling functional gene diversity mirrors phosphorus transformation during chicken manure composting

Elucidating ecological mechanism underlying phosphorus transformation mediated by phosphate-solubilizing bacteria (PSB) during manure composting is an important but rarely investigated subject. The research objective is to disentangle ecological functions of the inoculation of PSB Pseudomonas sp. WWJ-22 during chicken manure composting based on gene quantification and amplicon sequencing. There are large dynamic changes in phosphorus fractions, gene abundances, and bacterial community structure. The PSB addition notably increased available phosphorus from 0.29–0.89 g kg−1 to 0.49–1.39 g kg−1 and significantly affected phosphorus fractionation. The PSB inoculation significantly affected composition of nutrient-cycling functional genes (NCFGs), and notably influenced bacterial community composition and function. Compost bacteria showed significant phylogenetic signals in response to phosphorus fractions, and stochastic processes dominated bacterial community assembly. Results emphasized that PSB addition increased functional redundancy, phylogenetic conservatism, and stochasticity-dominated assembly of bacterial community. Overall, findings highlight NCFG diversity can be a bio-indicator to mirror phosphorus transformation.