Coupled 3D (J ≥ 0) Time-Dependent Wave Packet Calculation for the F + H2 Reaction on Accurate Ab Initio Multi-State Diabatic Potential Energy Surfaces.

We had calculated adiabatic potential energy surfaces (PESs), nonadiabatic, and spin-orbit (SO) coupling terms among the lowest three electronic states (12A', 22A', and 12A″) of the F + H2 system using the multireference configuration interaction (MRCI) level of theory, and the adiabatic-to-diabatic transformation equations were solved to formulate the diabatic Hamiltonian matrix [J. Chem. Phys. 2020, 153, 174301] for the entire region of the nuclear configuration space. The accuracy of such diabatic PESs is explored by performing scattering calculations to evaluate integral cross sections (ICSs) and rate constants. The nonadiabatic and SO effects are studied by utilizing coupled 3D time-dependent wave packet formalism with zero and nonzero total angular momentum on multiple adiabatic/diabatic surfaces calculation. We depict the convergence profiles of reaction probabilities for the reactive as well as nonreactive processes on various electronic states at different collision energies with respect to total angular momentum including all helicity quantum numbers. Finally, total ICSs are calculated as functions of collision energies for the initial rovibrational state (v = 0, j = 0) of the H2 molecule along with the temperature-dependent rate coefficient, where those quantities are compared with previous theoretical and experimental results.

Double-stranded RNA targeting white mold Sclerotinia sclerotiorum argonaute 2 for disease control via spray-induced gene silencing.

Sclerotinia sclerotiorum, the causal agent of white mold infection, is a cosmopolitan fungal pathogen that causes major yield losses in many economically important crops. Spray induced gene silencing (SIGS) has recently been shown to be a promising alternative method for controlling plant diseases. Based on our prior research, we focus on developing SIGS approach to control white mold by silencing S. sclerotiorum argonaute 2 (SsAgo2), a crucial part of the fungal small RNA pathway. We compared the lesion size as a result of targeting each ~500-bp segments of SsAgo2 from 5' to 3' and found that targeting the PIWI/ RNaseH domain of SsAgo2 is most effective. External application of double-stranded RNA (dsRNA) suppressed white mold infection using either in vitro or in vivo transcripts was determined at the rate of 800 ng/0.2cm2 area with a downregulation of SsAgo2 from infected leaf tissue confirmed by RT-qPCR. Furthermore, magnesium/iron-layered double hydroxides (MgFe-LDH) nanosheets loaded with in vitro and in vivo transcribed dsRNA segments significantly reduced the rate of S. sclerotiorum lesion expansion. In vivo produced dsRNA targeting the PIWI/RNaseH domain of the SsAgo2 transcript showed increased efficacy in reducing the white mold symptoms of S. sclerotiorum when combined with LDH nanosheets. This approach is promising to produce a large scale of dsRNA that can be deployed as an environmentally friendly fungicide to manage white mold infections in the field.

Ultramicroporous Lonsdaleite Topology MOF with High Propane Uptake and Propane/Methane Selectivity for Propane Capture from Simulated Natural Gas.

Propane (C3H8) is a widely used fuel gas. Metal-organic framework (MOF) physisorbents that are C3H8 selective offer the potential to significantly reduce the energy footprint for capturing C3H8 from natural gas, where C3H8 is typically present as a minor component. Here we report the C3H8 recovery performance of a previously unreported lonsdaleite, lon, topology MOF, a chiral metal-organic material, [Ni(S-IEDC)(bipy)(SCN)]n, CMOM-7. CMOM-7 was prepared from three low-cost precursors: Ni(SCN)2, S-indoline-2-carboxylic acid (S-IDECH), and 4,4'-bipyridine (bipy), and its structure was determined by single crystal X-ray crystallography. Pure gas adsorption isotherms revealed that CMOM-7 exhibited high C3H8 uptake (2.71 mmol g-1) at 0.05 bar, an indication of a higher affinity for C3H8 than both C2H6 and CH4. Dynamic column breakthrough experiments afforded high purity C3H8 capture from a gas mixture comprising C3H8/C2H6/CH4 (v/v/v = 5/10/85). Despite the dilute C3H8 stream, CMOM-7 registered a high dynamic uptake of C3H8 and a breakthrough time difference between C3H8 and C2H6 of 79.5 min g-1, superior to those of previous MOF physisorbents studied under the same flow rate. Analysis of crystallographic data and Grand Canonical Monte Carlo simulations provides insight into the two C3H8 binding sites in CMOM-7, both of which are driven by C-H···π and hydrogen bonding interactions.

Aquaporins: a vital nexus in H2O2-gasotransmitter signaling.

Land plants have evolved with a complex mechanism of water uptake facilitated by the activity of aquaporins under normal and challenging environments. However, we lack a clear understanding of its interactions with reactive oxygen species, particularly hydrogen peroxide (H2O2) and the gasotransmitters nitric oxide (NO) and hydrogen sulfide (H2S), under oxidative stress. Here, we assess the crosstalk of aquaporin function, H2O2 homeostasis, and NO-H2S signaling in plants and provide a computational prediction of cysteine-based oxidative post-translational modifications (oxiPTMs) in plant aquaporins. We propose that aquaporin activity could be regulated by three major oxiPTMs, S-nitrosation, S-sulfenylation, and persulfidation, mediated by NO, H2O2, and H2S, respectively. Therefore, aquaporins might be key players in the gasotransmitter-mediated long-distance oxidative stress signals in plant cells.

Crystal Engineering of a New Hexafluorogermanate Pillared Hybrid Ultramicroporous Material Delivers Enhanced Acetylene Selectivity.

Hybrid ultramicroporous materials (HUMs), metal-organic platforms that incorporate inorganic pillars, are a promising class of porous solids. A key area of interest for such materials is gas separation, where HUMs have already established benchmark performances. Thanks to their ready compositional modularity, we report the design and synthesis of a new HUM, GEFSIX-21-Cu, incorporating the ligand pypz (4-(3,5-dimethyl-1H-pyrazol-4-yl)pyridine, 21) and GeF62- pillaring anions. GEFSIX-21-Cu delivers on two fronts: first, it displays an exceptionally high C2H2 adsorption capacity (≥5 mmol g-1) which is paired with low uptake of CO2 (<2 mmol g-1), and, second, a low enthalpy of adsorption for C2H2 (ca. 32 kJ mol-1). This combination is rarely seen in the C2H2 selective physisorbents reported thus far, and not observed in related isostructural HUMs featuring pypz and other pillaring anions. Dynamic column breakthrough experiments for 1:1 and 2:1 C2H2/CO2 mixtures revealed GEFSIX-21-Cu to selectively separate C2H2 from CO2, yielding ≥99.99% CO2 effluent purities. Temperature-programmed desorption experiments revealed full sorbent regeneration in <35 min at 60 °C, reinforcing HUMs as potentially technologically relevant materials for strategic gas separations.

Nanovehicles for melatonin: a new journey for agriculture.

The important role of melatonin in plant growth and metabolism together with recent advances in the potential use of nanomaterials have opened up interesting applications in agriculture. Various nanovehicles have been explored as melatonin carriers in animals, and it is now important to explore their application in plants. Recent findings have substantiated the use of silicon and chitosan nanoparticles (NPs) in targeting melatonin to plant tissues. Although melatonin is an amphipathic molecule, nanocarriers can accelerate its uptake and transport to various plant organs, thereby relieving stress and improving plant shelf-life in the post-harvest stages. We review the scope and biosafety concerns of various nanomaterials to devise novel methods for melatonin application in crops and post-harvest products.

Photoelectron spectra of benzene: Can path dependent diabatic surfaces provide unique observables?

While carrying out Beyond Born-Oppenheimer theory based diabatization, the solutions of adiabatic-to-diabatic transformation equations depend on the paths of integration over two-dimensional cross-sections of multi-dimensional space of nuclear degrees of freedom. It is shown that such path-dependent solutions leading to diabatic potential energy surface matrices computed along any two different paths are related through an orthogonal matrix, and thereby, those surface matrices should provide unique observables. While exploring the numerical validity of the theoretical framework, we construct diabatic Hamiltonians for the five low-lying electronic states (X̃2E1g, B̃2E2g, and C̃2A2u) of benzene radical cation (C6H6+) along three different approaches of contour integration over two dimensional nuclear planes constituted by seven non-adiabatically active normal modes. Three different diabatic surface matrices are further employed to generate the photoelectron spectra of the benzene molecule (C6H6). It is interesting to note that the spectral peak positions and intensity patterns for all three cases are almost close to each other and also exhibit very good agreement with the experimental results.

Effect of Extra-Framework Anion Substitution on the Properties of a Chiral Crystalline Sponge.

Chiral metal-organic materials, CMOMs, are of interest as they can offer selective binding sites for chiral guests. Such binding sites can enable CMOMs to serve as chiral crystalline sponges (CCSs) to determine molecular structure and/or purify enantiomers. We recently reported on the chiral recognition properties of a homochiral cationic diamondoid, dia, network {[Ni(S-IDEC)(bipy)(H2O)][NO3]}n (S-IDEC = S-indoline-2-carboxylicate, bipy = 4,4'-bipyridine), CMOM-5[NO3]. The modularity of CMOM-5[NO3] means there are five feasible approaches to fine-tune structures and properties via substitution of one or more of the following components: metal cation (Ni2+); bridging ligand (S-IDEC); linker (bipy); extra-framework anion (NO3-); and terminal ligand (H2O). Herein, we report the effect of anion substitution on the CCS properties of CMOM-5[NO3] by preparing and characterizing {[Ni(S-IDEC)(bipy)(H2O)][BF4]}n, CMOM-5[BF4]. The chiral channels in CMOM-5[BF4] enabled it to function as a CCS for determination of the absolute crystal structures of both enantiomers of three chiral compounds: 1-phenyl-1-butanol (1P1B); methyl mandelate (MM); ethyl mandelate (EM). Chiral resolution experiments revealed CMOM-5[BF4] to be highly selective toward the S-isomers of MM and EM with enantiomeric excess, ee, values of 82.6 and 78.4%, respectively. The ee measured for S-EM surpasses the 64.3% exhibited by [DyNaL(H2O)4] 6H2O and far exceeds that of CMOM-5[NO3] (6.0%). Structural studies of the binding sites in CMOM-5[BF4] provide insight into their high enantioselectivity.

Water vapour induced structural flexibility in a square lattice coordination network.

Herein, we introduce a new square lattice topology coordination network, sql-(1,3-bib)(ndc)-Ni, with three types of connection and detail its gas and vapour induced phase transformations. Exposure to humidity resulted in an S-shaped isotherm profile, suggesting potential utility of such materials as desiccants.

Trapping and exciton-exciton annihilation assisted ultrafast carrier dynamics in nanosheets of 2H-MoSe2 and Cr doped 1T/2H-MoSe2.

Nanosheets of transition metal dichalcogenides with prospects of photocatalysis and optoelectronics applications have significant potential in device fabrication due to their low-cost production and easily controllable morphology. Here, non-degenerate pump-probe differential transmission studies with varying pump-fluence have been carried out on single-phase 2H-MoSe2 and mixed-phase 1T/2H-MoSe2 nanosheets to characterize their excited carrier dynamics. For both the samples, the differential probe transmission data show photo-induced bleaching at earlier pump-probe delay followed by photo-induced absorption unveiling signatures of exciton-state filling, exciton trapping, defect-mediated photo-induced probe absorption and recombination of defect bound excitons. The exciton trapping and photo-induced absorption by the trapped-carriers are estimated to occur with time constant of ∼430 to 500 fs based on multi-exponential modelling of the differential transmission till pump-probe delay of ∼3.5 ps. Biexponential modeling of the subsequent slow-recovery of the negative differential transmission at pump-probe delay ≳3.5 ps reveals that the exciton recombination happens via two distinct decay channels with ∼25 to 55 ps (τ1) and ≳1 ns (τ2) time constants. Pump-fluence dependent reduction in τ1 and further modelling of exciton population using higher order kinetic rate equation reveals that the two-body exciton-exciton annihilation governs the exciton recombination initially with a decay rate of ∼10-8 cm3s-1. The detailed analysis suggests that the fraction of total excitons that decay via long decay channel decreases with increasing exciton density for 2H-MoSe2, in contrast to 1T/2H-MoSe2 where the fraction of excitons decaying via long decay channel remains constant.

Crystal Engineering of a Chiral Crystalline Sponge That Enables Absolute Structure Determination and Enantiomeric Separation.

Chiral metal-organic materials (CMOMs), can offer molecular binding sites that mimic the enantioselectivity exhibited by biomolecules and are amenable to systematic fine-tuning of structure and properties. Herein, we report that the reaction of Ni(NO3)2, S-indoline-2-carboxylic acid (S-IDECH), and 4,4'-bipyridine (bipy) afforded a homochiral cationic diamondoid, dia, network, [Ni(S-IDEC)(bipy)(H2O)][NO3], CMOM-5. Composed of rod building blocks (RBBs) cross-linked by bipy linkers, the activated form of CMOM-5 adapted its pore structure to bind four guest molecules, 1-phenyl-1-butanol (1P1B), 4-phenyl-2-butanol (4P2B), 1-(4-methoxyphenyl)ethanol (MPE), and methyl mandelate (MM), making it an example of a chiral crystalline sponge (CCS). Chiral resolution experiments revealed enantiomeric excess, ee, values of 36.2-93.5%. The structural adaptability of CMOM-5 enabled eight enantiomer@CMOM-5 crystal structures to be determined. The five ordered crystal structures revealed that host-guest hydrogen-bonding interactions are behind the observed enantioselectivity, three of which represent the first crystal structures determined of the ambient liquids R-4P2B, S-4P2B, and R-MPE.

Low tension recruits the yeast Aurora B protein Ipl1 to centromeres in metaphase.

Accurate genome segregation in mitosis requires that all chromosomes are bioriented on the spindle. Cells monitor biorientation by sensing tension across sister centromeres. Chromosomes that are not bioriented have low centromere tension, which allows Aurora B (yeast Ipl1) to perform error correction that locally loosens kinetochore-microtubule attachments to allow detachment of microtubules and fresh attempts at achieving biorientation. However, it is not known whether low tension recruits Aurora B to centromeres or, alternatively, whether low tension directly activates Aurora B already localized at centromeres. In this work, we experimentally induced low tension in metaphase Saccharomyces cerevisiae yeast cells, then monitored Ipl1 localization. We find low tension recruits Ipl1 to centromeres. Furthermore, low tension-induced Ipl1 recruitment depended on Bub1, which is known to provide a binding site for Ipl1. In contrast, Top2, which can also recruit Ipl1 to centromeres, was not required. Our results demonstrate cells are sensitive to low tension at centromeres and respond by actively recruiting Ip1l for error correction.

Room Temperature Synthesis Mediated Porphyrinic NanoMOF Enables Benchmark Electrochemical Biosensing.

Leveraging size effects, nanoparticles of metal-organic frameworks, nanoMOFs, have recently gained traction, amplifying their scopes in electrochemical sensing. However, their synthesis, especially under eco-friendly ambient conditions remains an unmet challenge. Herein, an ambient and fast secondary building unit (SBU)-assisted synthesis (SAS) route to afford a prototypal porphyrinic MOF, Fe-MOF-525 is introduced. Albeit the benign room temperature conditions, Fe-MOF-525(SAS) nanocrystallites obtained are of ≈30 nm size, relatively smaller than the ones conventional solvothermal methods elicit. Integrating Fe-MOF-525(SAS) as a thin film on a conductive indium tin oxide (ITO) surface affords Fe-MOF-525(SAS)/ITO, an electrochemical biosensor. Synergistic confluence of modular MOF composition, analyte-specific redox metalloporphyrin sites, and crystal downsizing contribute to its benchmark voltammetric uric acid (UA) sensing. Showcasing a wide linear range of UA detection with high sensitivity and low detection limit, this SAS strategy coalesces ambient condition synthesis and nanoparticle size control, paving a green way to advanced sensors.

Robust microtubule dynamics facilitate low-tension kinetochore detachment in metaphase.

During mitosis, sister chromatids are stretched apart at their centromeres via their attachment to oppositely oriented kinetochore microtubules. This stretching generates inwardly directed tension across the separated sister centromeres. The cell leverages this tension signal to detect and then correct potential errors in chromosome segregation, via a mechanical tension signaling pathway that detaches improperly attached kinetochores from their microtubules. However, the sequence of events leading up to these detachment events remains unknown. In this study, we used microfluidics to sustain and observe low-tension budding yeast metaphase spindles over multiple hours, allowing us to elucidate the tension history prior to a detachment event. We found that, under conditions in which kinetochore phosphorylation weakens low-tension kinetochore-microtubule connections, the mechanical forces produced via the dynamic growth and shortening of microtubules is required to efficiently facilitate detachment events. Our findings underscore the critical role of robust kinetochore microtubule dynamics in ensuring the fidelity of chromosome segregation during mitosis.

Melatonin involves hydrogen sulfide in the regulation of H+-ATPase activity, nitrogen metabolism, and ascorbate-glutathione system under chromium toxicity.

Contamination of soils with chromium (Cr) jeopardized agriculture production globally. The current study was planned with the aim to better comprehend how melatonin (Mel) and hydrogen sulfide (H2S) regulate antioxidant defense system, potassium (K) homeostasis, and nitrogen (N) metabolism in tomato seedlings under Cr toxicity. The data reveal that application of 30 µM Mel to the seedlings treated with 25 µM Cr has a positive effect on H2S metabolism that resulted in a considerable increase in H2S. Exogenous Mel improved phytochelatins content and H+-ATPase activity with an associated increase in K content as well. Use of tetraethylammonium chloride (K+-channel blocker) and sodium orthovanadate (H+-ATPase inhibitor) showed that Mel maintained K homeostasis through regulating H+-ATPase activity under Cr toxicity. Supplementation of the stressed seedlings with Mel substantially scavenged excess reactive oxygen species (ROS) that maintained ROS homeostasis. Reduced electrolyte leakage and lipid peroxidation were additional signs of Mel's ROS scavenging effects. In addition, Mel also maintained normal functioning of nitrogen (N) metabolism and ascorbate-glutathione (AsA-GSH) system. Improved level of N fulfilled its requirement for various enzymes that have induced resilience during Cr stress. Additionally, the AsA-GSH cycle's proper operation maintained redox equilibrium, which is necessary for the biological system to function normally. Conversely, 1 mM hypotaurine (H2S scavenger) abolished the Mel-effect and again Cr-induced impairment on the above-mentioned parameters was observed even in presence of Mel. Therefore, based on the observed findings, we concluded that Mel needs endogenous H2S to alleviate Cr-induced impairments in tomato seedlings.

Functions of Melatonin during Postharvest of Horticultural Crops.

Melatonin, a tryptophan-derived molecule, is endogenously generated in animal, plant, fungal and prokaryotic cells. Given its antioxidant properties, it is involved in a myriad of signaling functions associated with various aspects of plant growth and development. In higher plants, melatonin (Mel) interacts with plant regulators such as phytohormones, as well as reactive oxygen and nitrogen species including hydrogen peroxide (H2O2), nitric oxide (NO) and hydrogen sulfide (H2S). It shows great potential as a biotechnological tool to alleviate biotic and abiotic stress, to delay senescence and to conserve the sensory and nutritional quality of postharvest horticultural products which are of considerable economic importance worldwide. This review provides a comprehensive overview of the biochemistry of Mel, whose endogenous induction and exogenous application can play an important biotechnological role in enhancing the marketability and hence earnings from postharvest horticultural crops.

Buried island transposition flap for joint Plastic-Neurosurgical management of spinal wound dehiscence - a technical note and single Centre experience.

INTRODUCTION: Spinal surgical wound infection can lead to tissue voids between the spine and skin that can be difficult to reconstruct. Previously described techniques include myocutaneous flaps or perforator based fasciocutaneous flaps. However, these procedures can be time-consuming and surgically challenging. AIMS: This study aimed to assess the effectiveness of a novel technique employing a buried island transposition (BIT) flap, for the repair of non-irradiated dehisced spinal wounds. METHODS: Fifteen patients with failed conservative management of infected midline posterior spinal wounds, underwent wound repair using a local buried islanded de-epithelialized double-breasted fasciocutaneous transposition flap, performed by joint input from the neurosurgical and plastic surgical teams. RESULTS: Mean age was 58 years (range, 31-76 years) with male-to-female ratio of 8:7. The BIT flap was used to repair four wounds in the cervical spine with underlying fixation; four wounds in the thoracic spine with underlying fixation; and seven wounds in the lumbar-sacral spine, of which three had underlying fixation. Pre-operatively, each of the wounds were either dehiscent with exposed hardware, or had large defects unsuitable for primary closure following debridement. There was no procedure-related mortality. All patients demonstrated good wound healing with no subsequent repeat surgery or removal of spinal fixation at mean 24-month follow-up. CONCLUSION: We successfully used a novel buried island transposition flap that has not previously been described in repair of spinal wounds. This technique, which led in all cases to good wound healing and prevented removal of metalwork, has comparable efficacy but increased ease of use compared to traditional techniques. It requires redundant skin at the wound site.

Quantitative proteomics of tau and Aß in detergent fractions from Alzheimer's disease brains.

The two hallmarks of Alzheimer's disease (AD) are amyloid-ß (Aß) plaques and neurofibrillary tangles marked by phosphorylated tau. Increasing evidence suggests that aggregating Aß drives tau accumulation, a process that involves synaptic degeneration leading to cognitive impairment. Conversely, there is a realization that non-fibrillar (oligomeric) forms of Aß mediate toxicity in AD. Fibrillar (filamentous) aggregates of proteins across the spectrum of the primary and secondary tauopathies were the focus of recent structural studies with a filament structure-based nosologic classification, but less emphasis was given to non-filamentous co-aggregates of insoluble proteins in the fractions derived from post-mortem human brains. Here, we revisited sarkosyl-soluble and -insoluble extracts to characterize tau and Aß species by quantitative targeted mass spectrometric proteomics, biochemical assays, and electron microscopy. AD brain sarkosyl-insoluble pellets were greatly enriched with Aß42 at almost equimolar levels to N-terminal truncated microtubule-binding region (MTBR) isoforms of tau with multiple site-specific post-translational modifications (PTMs). MTBR R3 and R4 tau peptides were most abundant in the sarkosyl-insoluble materials with a 10-fold higher concentration than N-terminal tau peptides. This indicates that the major proportion of the enriched tau was the aggregation-prone N-terminal and proline-rich region (PRR) of truncated mixed 4R and 3R tau with more 4R than 3R isoforms. High concentration and occupancies of site-specific phosphorylation pT181 (~22%) and pT217 (~16%) (key biomarkers of AD) along with other PTMs in the PRR and MTBR indicated a regional susceptibility of PTMs in aggregated tau. Immunogold labelling revealed that tau may exist in globular non-filamentous form (N-terminal intact tau) co-localized with Aß in the sarkosyl-insoluble pellets along with tau filaments (N-truncated MTBR tau). Our results suggest a model that Aß and tau interact forming globular aggregates, from which filamentous tau and Aß emerge. These characterizations contribute towards unravelling the sequence of events which lead to end-stage AD changes.

Oxonium Ion-Guided Optimization of Ion Mobility-Assisted Glycoproteomics on the timsTOF Pro.

Spatial separation of ions in the gas phase, providing information about their size as collisional cross-sections, can readily be achieved through ion mobility. The timsTOF Pro (Bruker Daltonics) series combines a trapped ion mobility device with a quadrupole, collision cell, and a time-of-flight analyzer to enable the analysis of ions at great speed. Here, we show that the timsTOF Pro is capable of physically separating N-glycopeptides from nonmodified peptides and producing high-quality fragmentation spectra, both beneficial for glycoproteomics analyses of complex samples. The glycan moieties enlarge the size of glycopeptides compared with nonmodified peptides, yielding a clear cluster in the mobilogram that, next to increased dynamic range from the physical separation of glycopeptides and nonmodified peptides, can be used to make an effective selection filter for directing the mass spectrometer to analytes of interest. We designed an approach where we (1) focused on a region of interest in the ion mobilogram and (2) applied stepped collision energies to obtain informative glycopeptide tandem mass spectra on the timsTOF Pro:glyco-polygon-stepped collision energy-parallel accumulation serial fragmentation. This method was applied to selected glycoproteins, human plasma- and neutrophil-derived glycopeptides. We show that the achieved physical separation in the region of interest allows for improved extraction of information from the samples, even at shorter liquid chromatography gradients of 15 min. We validated our approach on human neutrophil and plasma samples of known makeup, in which we captured the anticipated glycan heterogeneity (paucimannose, phosphomannose, high mannose, hybrid and complex glycans) from plasma and neutrophil samples at the expected abundances. As the method is compatible with off-the-shelve data acquisition routines and data analysis software, it can readily be applied by any laboratory with a timsTOF Pro and is reproducible as demonstrated by a comparison between two laboratories.