On the covalent nature of lysine polyphosphorylation.

Post-translational modifications of proteins (PTMs) introduce an extra layer of complexity to cellular regulation. Although phosphorylation of serine, threonine, and tyrosine residues is well-known as PTMs, lysine is, in fact, the most heavily modified amino acid, with over 30 types of PTMs on lysine having been characterized. One of the most recently discovered PTMs on lysine residues is polyphosphorylation, which sees linear chains of inorganic polyphosphates (polyP) attached to lysine residues. The labile nature of phosphoramidate bonds raises the question of whether this modification is covalent in nature. Here, we used buffers with very high ionic strength, which would disrupt any non-covalent interactions, and confirmed that lysine polyphosphorylation occurs covalently on proteins containing PASK domains (polyacidic, serine-, and lysine-rich), such as the budding yeast protein nuclear signal recognition 1 (Nsr1) and the mammalian protein nucleolin. This Matters Arising Response paper addresses the Neville et al. (2024) Matters Arising paper, published concurrently in Molecular Cell.

Polyphosphate kinase-1 regulates bacterial and host metabolic pathways involved in pathogenesis of Mycobacterium tuberculosis.

Inorganic polyphosphate (polyP) is primarily synthesized by Polyphosphate Kinase-1 (PPK-1) and regulates numerous cellular processes, including energy metabolism, stress adaptation, drug tolerance, and microbial pathogenesis. Here, we report that polyP interacts with acyl CoA carboxylases, enzymes involved in lipid biosynthesis in Mycobacterium tuberculosis. We show that deletion of ppk-1 in M. tuberculosis results in transcriptional and metabolic reprogramming. In comparison to the parental strain, the Δppk-1 mutant strain had reduced levels of virulence-associated lipids such as PDIMs and TDM. We also observed that polyP deficiency in M. tuberculosis is associated with enhanced phagosome-lysosome fusion in infected macrophages and attenuated growth in mice. Host RNA-seq analysis revealed decreased levels of transcripts encoding for proteins involved in either type I interferon signaling or formation of foamy macrophages in the lungs of Δppk-1 mutant-infected mice relative to parental strain-infected animals. Using target-based screening and molecular docking, we have identified raloxifene hydrochloride as a broad-spectrum PPK-1 inhibitor. We show that raloxifene hydrochloride significantly enhanced the activity of isoniazid, bedaquiline, and pretomanid against M. tuberculosis in macrophages. Additionally, raloxifene inhibited the growth of M. tuberculosis in mice. This is an in-depth study that provides mechanistic insights into the regulation of mycobacterial pathogenesis by polyP deficiency.

Hybrid organic-inorganic structures trigger the formation of primitive cell-like compartments.

Alkaline hydrothermal vents have become a candidate setting for the origins of life on Earth and beyond. This is due to several key features including the presence of gradients of temperature, redox potential, pH, the availability of inorganic minerals, and the existence of a network of inorganic pore spaces that could have served as primitive compartments. Chemical gardens have long been used as experimental proxies for hydrothermal vents. This paper investigates-10pc]Please note that the spelling of the following author name in the manuscript differs from the spelling provided in the article metadata: Richard J. G. Löffler. The spelling provided in the manuscript has been retained; please confirm. a set of prebiotic interactions between such inorganic structures and fatty alcohols. The integration of a medium-chain fatty alcohol, decanol, within these inorganic minerals, produced a range of emergent 3 dimensions structures at both macroscopic and microscopic scales. Fatty alcohols can be considered plausible prebiotic amphiphiles that might have assisted the formation of protocellular structures such as vesicles. The experiments presented herein show that neither chemical gardens nor decanol alone promote vesicle formation, but chemical gardens grown in the presence of decanol, which is then integrated into inorganic mineral structures, support vesicle formation. These observations suggest that the interaction of fatty alcohols and inorganic mineral structures could have played an important role in the emergence of protocells, yielding support for the evolution of living cells.

Photon Upconversion at Organic-Inorganic Interfaces.

Photon upconversion is a process that combines low-energy photons to form useful high-energy photons. There are potential applications in photovoltaics, photocatalysis, biological imaging, etc. Semiconductor quantum dots (QDs) are promising for the absorption of these low-energy photons due to the high extinction coefficient of QDs, especially in the near infrared (NIR). This allows the intriguing use of diffuse light sources such as solar irradiation. In this review, we describe the development of this organic-QD upconversion platform based on triplet-triplet annihilation, focusing on the dark exciton in QDs with triplet character. Then we introduce the underlying energy transfer steps, starting from QD triplet photosensitization, triplet exciton transport, triplet-triplet annihilation, and ending with the upconverted emission. Design principles to improve the total upconversion efficiency are presented. We end with limitations in current reports and proposed future directions. This review provides a guide for designing efficient organic-QD upconversion platforms for future applications, including overcoming the Shockley-Queisser limit for more efficient solar energy conversion, NIR-based phototherapy, and diagnostics in vivo.

The landscape of nanoparticle-based siRNA delivery and therapeutic development.

Five small interfering RNA (siRNA)-based therapeutics have been approved by the Food and Drug Administration (FDA), namely patisiran, givosiran, lumasiran, inclisiran, and vutrisiran. Besides, siRNA delivery to the target site without toxicity is a big challenge for researchers, and naked-siRNA delivery possesses several challenges, including membrane impermeability, enzymatic degradation, mononuclear phagocyte system (MPS) entrapment, fast renal excretion, endosomal escape, and off-target effects. The siRNA therapeutics can silence any disease-specific gene, but their intracellular and extracellular barriers limit their clinical applications. For this purpose, several modifications have been employed to siRNA for better transfection efficiency. Still, there is a quest for better delivery systems for siRNA delivery to the target site. In recent years, nanoparticles have shown promising results in siRNA delivery with minimum toxicity and off-target effects. Patisiran is a lipid nanoparticle (LNP)-based siRNA formulation for treating hereditary transthyretin-mediated amyloidosis that ultimately warrants the use of nanoparticles from different classes, especially lipid-based nanoparticles. These nanoparticles may belong to different categories, including lipid-based, polymer-based, and inorganic nanoparticles. This review briefly discusses the lipid, polymer, and inorganic nanoparticles and their sub-types for siRNA delivery. Finally, several clinical trials related to siRNA therapeutics are addressed, followed by the future prospects and conclusions.

New paradigms in actomyosin energy transduction: Critical evaluation of non-traditional models for orthophosphate release.

Release of the ATP hydrolysis product ortophosphate (Pi) from the active site of myosin is central in chemo-mechanical energy transduction and closely associated with the main force-generating structural change, the power-stroke. Despite intense investigations, the relative timing between Pi-release and the power-stroke remains poorly understood. This hampers in depth understanding of force production by myosin in health and disease and our understanding of myosin-active drugs. Since the 1990s and up to today, models that incorporate the Pi-release either distinctly before or after the power-stroke, in unbranched kinetic schemes, have dominated the literature. However, in recent years, alternative models have emerged to explain apparently contradictory findings. Here, we first compare and critically analyze three influential alternative models proposed previously. These are either characterized by a branched kinetic scheme or by partial uncoupling of Pi-release and the power-stroke. Finally, we suggest critical tests of the models aiming for a unified picture.

The Role of Serine/Threonine-Specific Protein Kinases in Cyanobacteria - SpkB Is Involved in Acclimation to Fluctuating Conditions in Synechocystis sp. PCC 6803.

Protein phosphorylation via serine/threonine protein kinases (Spk) is a widespread mechanism to adjust cellular processes toward changing environmental conditions. To study their role(s) in cyanobacteria, we investigated a collection of 11 completely segregated spk mutants among the 12 annotated Spks in the model cyanobacterium Synechocystis sp. PCC 6803. Screening of the mutant collection revealed that especially the mutant defective in SpkB encoded by slr1697 showed clear deviations regarding carbon metabolism, that is, reduced growth rates at low CO2 or in the presence of glucose, and different glycogen accumulation patterns compared to WT. Alterations in the proteome of ΔspkB indicated changes of the cell surface but also metabolic functions. A phospho-proteome analysis revealed the absence of any phosphorylation in two proteins, while decreased phosphorylation of the carboxysome-associated protein CcmM and increased phosphorylation of the allophycocyanin alpha subunit ApcA was detected in ΔspkB. Furthermore, the regulatory PII protein appeared less phosphorylated in the mutant compared to WT, which was verified in Western blot experiments, indicating a clearly delayed PII phosphorylation in cells shifted from nitrate-containing to nitrate-free medium. Our results indicate that SpkB is an important regulator in Synechocystis that is involved in phosphorylation of the PII protein and additional proteins.

Organic molecular dynamics and charge-carrier lifetime in lead iodide perovskite MAPbI3.

The long charge carrier lifetime of the hybrid organic-inorganic perovskites (HOIPs) is the key for their remarkable performance as a solar cell material. The microscopic mechanism for the long lifetime is still in debate. Here, by using a muon spin relaxation technique that probes the fluctuation of local magnetic fields, we show that the muon depolarization rate (Δ) of a prototype HOIP methylammonium lead iodide (MAPbI3) shows a sharp decrease with increasing temperature in two steps above 120 K and 190 K across the structural transition from orthorhombic to tetragonal structure at 162 K. Our analysis shows that the reduction of Δ is quantitatively in agreement with the expected behavior due to the rapid development of methyl ammonium (MA) jumping rotation around the C 3 and C 4 symmetry axes. Our results provide direct evidence for the intimate relation between the rotation of the electric dipoles of MA molecules and the charge carrier lifetime in HOIPs.

Fabrication of an Ultrastrong Formaldehyde-Free Wood Adhesive with an Organic-Inorganic Cross-Linking Network.

The wood industry faces challenges in producing eco-friendly, high-performance, and formaldehyde-free adhesives. In this study, carboxylated styrene-butadiene rubber (XSBR) was blended with polyamidoamine-epichlorohydrin (PAE) resin, and a controlled amount of CaCO3 powder was incorporated to create an adhesive with exceptional strength. The resulting three-layer plywood demonstrated remarkable dry and wet shear strengths of 3.09 and 2.36 MPa, respectively, and of 2.27 MPa after boiling water tests, comparable to that of phenolic resins. Additionally, the adhesive exhibited strong adhesion across various materials including glass, metal, etc. This exceptional performance was due to two primary factors: (1) the high-density chemical cross-linking reaction and the physical entanglement between XSBR and PAE; (2) the organic-inorganic hybrid involving metal ion complexation developed by CaCO3, which fostered molecular chain connections and enhanced the adhesive-material interface. These findings offer valuable references for further research in the field of wood adhesives.

Nuclear Quantum Effects Accelerate Charge Recombination but Boost the Stability of Inorganic Perovskites in Mild Humidity.

Experiments have demonstrated that mild humidity can enhance the stability of the CsPbBr3 perovskite, though the underlying mechanism remains unclear. Utilizing ab initio molecular dynamics, ring polymer molecular dynamics, and non-adiabatic molecular dynamics, our study reveals that nuclear quantum effects (NQEs) play a crucial role in stabilizing the lattice rigidity of the perovskite while simultaneously shortening the charge carrier lifetime. NQEs reduce the extent of geometric disorder and the number of atomic fluctuations, diminish the extent of hole localization, and thereby improve the electron-hole overlap and non-adiabatic coupling. Concurrently, these effects significantly suppress phonon modes and slow decoherence. As a result, these factors collectively accelerate charge recombination by a factor of 1.42 compared to that in scenarios excluding NQEs. The resulting sub-10 ns recombination time scales align remarkably well with experimental findings. This research offers novel insight into how moisture resistance impacts the stability and charge carrier lifetime in all-inorganic perovskites.

Hydrophobic Two-Dimensional Layered Superstructure of a Polyoxometalate Cluster as the Cathode Material for Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries hold promise for sustainable energy storage, yet challenges in finding high-performance cathode materials persist. Polyoxovanadates (POVs) are emerging as potential candidates due to their structural diversity and robust redox activity. Despite their potential, issues like dissolution in electrolytes, structural degradation, and byproduct accumulation persist. This work introduces a POV-based hydrophobic two-dimensional (2D) layered superstructure that addresses these challenges. The hydrophobic nature minimizes POV dissolution, enhancing structural stability and inhibiting phase transitions during cycling. The 2D arrangement ensures a larger surface area and improved electronic conductivity, resulting in faster kinetics and higher specific capacity. The superstructure demonstrates improved cycle life and an increased operating voltage, marking a significant advancement in POV-based cathode materials for aqueous zinc-ion batteries.

Influence of planting dates and fertilizer modules on yield of chrysanthemum and soil health.

BACKGROUND: Optimum planting date and appropriate fertilizer module are essential facets of chrysanthemum cultivation, to enhance quality yield, and improve soil health. A field-based study was undertaken over multiple growing seasons in 2022 and 2023, where six different planting dates, viz., P1:June 15, P2:June 30, P3:July 15, P4:July 30, P5:August 15 and P6:August 30 and two fertilizer modules, FM1:Jeevamrit @ 30 ml plant-1 and FM2:NPK @ 30 g m-2 were systematically examined using a Randomized Block Design (factorial), replicated thrice. RESULTS: P6 planting resulted in early bud formation (44.03 days) and harvesting stage (90.78 days). Maximum plant height (79.44 cm), plant spread (34.04 cm), cut stem length (68.40 cm), flower diameter (7.83 cm), stem strength (19.38˚), vase life (14.90 days), flowering duration (24.08 days), available soil N (314 kg ha-1), available P (37 kg ha-1), available K (347 kg ha-1), bacterial count (124.87 × 107 cfu g-1 soil), actinomycetes count (60.72 × 102 cfu g-1 soil), fungal count (30.95 × 102 cfu g-1 soil), microbial biomass (48.79 µg g-1 soil), dehydrogenase enzyme (3.64 mg TPF h-1 g-1 soil) and phosphatase enzyme (23.79 mol PNP h-1 g-1 soil) was recorded in P1 planting. Among the fertilization module, minimum days to bud formation (74.94 days) and days to reach the harvesting stage (120.95 days) were recorded with the application of NPK @30 g m-2. However, maximum plant height (60.62 cm), plant spread (23.10 cm), number of cut stems m-2 (43.88), cut stem length (51.34 cm), flower diameter (6.92 cm), stem strength (21.24˚), flowering duration (21.75 days), available soil N (317 kg ha-1), available P (37 kg ha-1) and available K (349 kg ha-1) were also recorded with the application of NPK @300 kg ha-1. Maximum vase life (13.87 days), OC (1.13%), bacterial count (131.65 × 107 cfu g-1 soil), actinomycetes count (60.89 × 102 cfu g-1 soil), fungal count (31.11 × 102 cfu g-1 soil), microbial biomass (51.27 µg g-1 soil), dehydrogenase enzyme (3.77 mg TPF h-1 g-1 soil) and phosphatase enzyme (21.72 mol PNP h-1 g-1 soil) were observed with the application of Jeevamrit @ 30 ml plant-1. CONCLUSION: Early planting (P1) and inorganic fertilization (NPK @ 30 g m-2) resulted in improved yield and soil macronutrient content. The soil microbial population and enzymatic activity were improved with the jeevamrit application. This approach highlights the potential for improved yield and soil health in chrysanthemum cultivation, promoting a more eco-friendly and economically viable agricultural model.

Extended benchmark set for lattice parameters of inorganic solids.

The development of novel methods in solid-state quantum chemistry necessitates reliable reference data sets for their assessment. The most fundamental solid-state property of interest is the crystal structure, quantified by the lattice parameters. In the last decade, several studies were conducted to assess theoretical approaches based on the agreement of calculated lattice parameters with respect to experiment as a measure. However, most of these studies used a limited number of reference systems with high symmetry. The present work offers a more comprehensive reference benchmark denoted as Sol337LC, which consists of 337 inorganic compounds with 553 symmetry-inequivalent lattice parameters, representing every element of the periodic table for atomic numbers between 1 and 86, except noble gases, the radioactive elements and lanthanoids. The reference values were taken from earlier benchmarks and from measurements at very low temperature or extrapolation to 0 K. The experimental low-temperature lattice parameters were then corrected for zero-point energy effects via the quasi-harmonic approximation for direct comparison with quantum-chemical optimized structures. A selection of standard density functional approximations was assessed for their deviations from the experimental reference data. The calculations were performed with the crystal orbital program CRYSTAL23, applying optimized atom-centered basis sets of triple-zeta plus polarization quality. The SCAN functional family and the global hybrid functional PW1PW, augmented with the D3 dispersion correction, were found to provide closest agreement with the Sol337LC reference data.

Strongly-Interacted NiSe2/NiFe2O4 Architectures Built Through Selective Atomic Migration as Catalysts for the Oxygen Evolution Reaction.

The interactions between the catalyst and support are widely used in many important catalytic reactions but the construction of strong interaction with definite microenvironments to understand the structure-activity relationship is still challenging. Here, strongly-interacted composites are prepared via selective exsolution of active NiSe2 from the host matrix of NiFe2O4 (S-NiSe2/NiFe2O4) taking advantage of the differences of migration energy, in which the NiSe2 possessed both high dispersion and small size. The characteristics of spatially resolved scanning transmission X-ray microscopy (STXM) coupled with analytical Mössbauer spectra for the surface and bulk electronic structures unveiled that this strongly interacted composite triggered more charge transfers from the NiSe2 to the host of NiFe2O4 while stabilizing the inherent atomic coordination of NiFe2O4. The obtained S-NiSe2/NiFe2O4 exhibits overpotentials of 290 mV at 10 mA cm-2 for oxygen evolution reaction (OER). This strategy is general and can be extended to other supported catalysts, providing a powerful tool for modulating the catalytic performance of strongly-interacted composites.

Network of Inorganic Nanocrystals Can Swell: Study of Swelling-Induced Surface Instability.

A unique organic-inorganic hybrid network composed of inorganic nanocores (ranging from semiconductors to metallic ones) interconnected through organic molecules can be produced by crosslinking the organic ligands of colloidal inorganic nanocrystals in assemblies. This work reports that this network, which is conventionally considered an inorganic film, can swell when exposed to a solvent because of the interaction between the solvent and the organic linkage within the network. Intriguingly, this work discovers that drying the solvent of the swollen organic-inorganic hybrid network can significantly affect the morphology owing to the swelling-induced compress stress, which is widely observed in various organic network systems. This work studies the surface instability of crosslinked organic-inorganic hybrid networks swollen by various organic solvents, which led to buckling delamination. Specifically, this work investigates the effects of the i) solvent-network interaction, ii) crosslinking density of the network, and iii) thickness of the film on the delamination behavior of the crosslinked network.

Design Strategy for Improving Detection Sensitivity in a Bromoplumbate Photochromic Semiconductor.

Reducing the dark current of photodetectors is an important strategy for enhancing the detection sensitivity, but hampered by the manufacturing cost due to the need for controlling the complex material composition and processing intricate interface. This study reports a new single-component photochromic semiconductor, [(HDMA)4(Pb3Br10)(PhSQ)2]n (1, HDMA = dimethylamine cation, PhSQ = 1-(4-sulfophenyl)-4,4'-bipyridinium), by introducing a redox-active monosubstituted viologen zwitterion into inorganic semiconducting skeleton. It features yellow to green coloration after UV irradiation with the sharply dropping intrinsic conductivity of 14.6-fold, and the photodetection detection sensitivity gain successfully doubles. The reason of decreasing conductivity originates from the increasing the band gap of the inorganic semiconducting component and formation of Frenkel excitons with strong Coulomb interactions, thereby decreasing the concentration of thermally excited intrinsic carriers.

Inorganic Oxide-Based "Hydrophobic-Hydrophilic-Hydrophobic" Separators Systems for Long-Life Zinc-Ion Batteries.

Hydrogen reduction reaction (HER) and corrosion limit the long-life cycle of zinc-ion batteries. However, hydrophilic separators are unable to prevent direct contact between water and electrodes, and hydrophobic separators have difficulty in transporting electrolytes. In this work, an inorganic oxide-based "hydrophobic-hydrophilic-hydrophobic" self-assembled separator system is proposed. The hydrophobic layer consists of a porous structure, which can isolate a large amount of free water to avoid HER and corrosion reactions, and can transport electrolyte by binding water. The middle hydrophilic layer acts as a storage layer consisting of the GF separator, storing large amounts of electrolyte for proper circulation. By using this structure separator, Zn||Zn symmetric cell achieve 2200 h stable cycle life at 5 mA cm-2 and 1mAh cm-2 and still shows a long life of 1800 h at 10 mA cm-2 and 1mAh cm-2. The assembled Zn||VO2 full cell displays high specific capacity and excellent long-term durability of 60.4% capacity retention after 1000 cycles at 2C. The assembled Zn||VO2 pouch full cell displays high specific capacity of 172.5mAh g-1 after 40 cycles at 0.5C. Changing the inorganic oxide materials, the hydrophobic-hydrophilic-hydrophobic structure of the separators still has excellent performance. This work provides a new idea for the engineering of water-based battery separators.

Controlling Nucleation and Crystallization of CsPbI3 Perovskites for Efficient Inverted Solar Cells.

The unfavorable morphology and high crystallization temperature (Tc) of inorganic perovskites pose a significant challenge to their widespread application in photovoltaics. In this study, an effective approach is proposed to enhance the morphology of cesium lead triiodide (CsPbI3) while lowering its Tc. By introducing dimethylammonium acetate into the perovskite precursor solution, a rapid nucleation stage is facilitated, and significantly enhances the crystal growth of the intermediate phase at low annealing temperatures, followed by a slow crystal growth stage at higher annealing temperatures. This results in a uniform and dense morphology in CsPbI3 perovskite films with enhanced crystallinity, simultaneously reducing the Tc from 200 to 150 °C. Applying this approach in positive-intrinsic-negative (p-i-n) inverted cells yields a high power conversion efficiency of 19.23%. Importantly, these cells exhibit significantly enhanced stability, even under stress at 85 °C.

Enhancing Pollutant Mineralization through Organic-Inorganic Defect-Transit Dual S-scheme with a Robust Internal Electric Field.

Achieving superior photomineralization of pollutants relies on a rational design of a dual S-scheme with a robust internal electric field (IEF). In this study, to tackle the low mineralization rate in type-II In2 O3 /In2 S3 (IO/IS) systems, an organic-inorganic dual S-scheme In2 O3 /PDI/In2 S3 (IO/PDI/IS) nanostructured photocatalyst is synthesized via a method combining solvent-induced self-assembly and electrostatic forces. Due to the unique energy band position and strong IEF, the photoinduced defect-transit dual S-scheme IO/PDI/IS facilitates the degradation of lignin and antibiotics. Notably, a promising mineralization rate of 80.9% for sodium lignosulfonate (SL) is achieved. The charge transport pathway of IO/PDI/IS are further validated through the analysis of in situ X-ray photoelectron spectroscopy (in situ XPS), density functional theory calculations, and radical trapping experiments. In-depth, two possible pathways for the photocatalytic degradation of lignin are proposed based on the intermediates monitored by liquid chromatography-mass spectrometry (LC-MS). This study presents a new strategy for the design of organic-inorganic dual S-scheme photocatalysts with a robust IEF for pollutant degradation.