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Mortierella alpina is a mold fungus that has gained attention for its positive correlation with soil health, plant growth, and applications as a crop biocontrol agent to suppress the threats of nematode pests. To date, the mechanisms underlying the protective traits of M. alpina against these plant parasites have remained elusive. Here we report that abundantly produced peptidic biosurfactants, malpinin A-D, exhibit robust inhibitory activity against nematodes. Nematode assays with malpinin congeners and chemically synthesized analogues revealed that the dehydro amino acid is critical for activity, whereas the N -terminal amino acid residues modulate the lipophilicity. Complementary imaging by fluorescence microscopy and Raman microspectroscopy, using externally fluorescence-labeled, semisynthetic malpinin or a biosynthetically alkyne-tagged probe generated by precursor-directed biosynthesis, visualized the translocation and enrichment of malpinin in the gut of the model nematode Caenorhabditis elegans . Our findings provide valuable insight into the use of M. alpina as a biocontrol agent, emphasizing the ecologically significant role of malpinins as a protective trait. In addition to solving a long-standing riddle, these findings have translational value for applications in agriculture.

Modifying the bacterial surface through grafting functional nanoparticles is a common strategy for programing bacteria. At this moment, the targeted nanoparticles face a dilemma of no multifunctional structure, high toxicity, and weak chemical driving forces, which restrict the broad practical applications. Like a multistage booster of a rocket, we propose a multistage covalent self-assembly strategy to protect, expand, and control the encapsulated shells of microbial cells via biocompatible hyper-cross-linked polymer nanoparticles (Bio-HCP NPs) with internal porosity and surface functional groups. The bacterial surface is enhanced with rich amino groups up to 10 10 per cell for specifically grafting nanoparticles. The arming bacteria after first-stage assembly can complete biocatalysis in a highly toxic environment, and as-prepared polymer aggregates (6-20 μm) after third-stage assembly can be accurately counted in an aerosol environment. This nanoparticle encapsulation exhibits strong cell viability from pollutants and specificity from impurity particles, holding promise for various complex application scenarios.

Interpretability is just as important as accuracy when it comes to complex models, especially in the context of deep learning models. Explainable artificial intelligence (XAI) approaches have been developed to address this problem. The literature on XAI for spectroscopy mainly emphasizes independent feature analysis with limited application of zone analysis. Individual feature analysis methods, such as shapley additive explanations (SHAP) and local interpretable model-agnostic explanations (LIME), have limitations due to their dependence on perturbations. These methods measure how AI models respond to sudden changes in the individual feature values. While they can help identify the most impactful features, the abrupt shifts introduced by replacing these values with zero or the expected ones may not accurately represent real-world scenarios. This can lead to mathematical and computational interpretations that are neither physically realistic nor intuitive to humans. Our proposed method does not rely on individual disturbances. Instead, it targets "spectral zones" to directly estimate the effect of group disturbances on a trained model. Consequently, factors such as sample size, hyperparameter selection, and other training-related considerations are not the primary focus of the XAI methods. To achieve this, we have developed a modified version of LIME and SHAP capable of performing group perturbations, enhancing explainability and realism while minimizing noise in the plots used for interpretability. Additionally, we employed an efficient approach to calculate spectral zones for complex spectra with indistinct spectral boundaries. Users can also define the zones themselves using their domain-specific knowledge.

Synthetic liposomes are widely used as drug delivery vehicles in biomedical treatments, such as for mRNA-based antiviral vaccines like those recently developed against SARS-CoV-2. Extracellular vesicles (EVs), which are naturally produced by cells, have emerged as a next-generation delivery system. However, key questions regarding their origin within cells remain unresolved. In this regard, plasma membrane vesicles (PMVs), which are essentially produced from the cellular plasma membrane (PM), present a promising alternative. Unfortunately, their properties relevant to biomedical applications have not be extensively studied. Therefore, we conducted a thorough investigation of the methods used in the production of PMVs. By leveraging advanced fluorescence techniques in microscopy and flow cytometry, we demonstrated a strong dependence of the physicochemical attributes of PMVs on the chemicals used during their production. Following established protocols employing chemicals such as paraformaldehyde (PFA), N- ethylmaleimide (NEM) or dl-dithiothreitol (DTT) and by developing a modified NEM-based method that involved a hypotonic shock step, we generated PMVs from THP-1 CD1d cells. We systematically compared key parameters such as vesicle output, their size distribution, vesicular content analysis, vesicular membrane lipid organization and the mobility of a transmembrane protein. Our results revealed distinct trends: PMVs isolated using NEM-based protocols closely resembled natural vesicles, whereas PFA induced significant molecular cross-linking, leading to notable changes in the biophysical properties of the vesicles. Furthermore, our novel NEM protocol enhanced the efficiency of PMV production. In conclusion, our study highlights the unique characteristics of chemically produced PMVs and offers insights into their potentially diverse yet valuable biological functions.

Matrix metalloproteinases (MMPs) are zinc-dependent proteinases that are capable of cleavage of extracellular matrix (ECM) proteins and enzymes and play an important role in lung dysfunction. Specifically, MMP-2 is produced in the lung by alveolar epithelial and endothelial cells and other immune cells, such as macrophages. MMP-2 regulatory pathway is initiated in alveolar macrophages during acute lung injury (ALI), which may increase pulmonary inflammation. Therefore, there is a critical need for fast and reliable techniques to track the acute respiratory distress syndrome (ARDS). Here, we describe near-infrared fluorescence resonance energy transfer (NI-FRET) MMP-2-based probe for the in vivo detection of ALI induced by lipopolysaccharides (LPS). LPS-induced MMP-2 was measured using near-infrared (NIR) imaging after 1, 2, 4, 5, and 24 h of LPS exposure. Our results were compared with the data obtained from ELISA and Western blotting, demonstrating that MMP-2 fluorescence probe provide a promising in vivo diagnostic tool for ALI/ARDS in infected mice., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Coherent Raman scattering microscopy utilizing bioorthogonal tagging approaches like isotope or alkyne labeling allows for a targeted monitoring of spatial distribution and dynamics of small molecules of interest in cells, tissues, and other complex biological matrices. To fully exploit this approach in terms of real-time monitoring of several Raman tags, e.g., to study drug uptake dynamics, extremely fast tunable lasers are needed. Here, we present a laser concept without moving parts and fully electronically controlled for the quasi-simultaneous acquisition of coherent anti-Stokes Raman scattering images at multiple Raman resonances. The laser concept is based on the combination of a low noise and spectrally narrow Fourier domain mode-locked laser seeding a compact four wave mixing-based high-power fiber-based optical parametric amplifier.

Nuclear medicine is expected to make major advances in cancer diagnosis and therapy; tumor-targeted radiopharmaceuticals preferentially eradicate tumors while causing minimal damage to healthy tissues. The current scope of nuclear medicine can be significantly expanded by integration with nanomedicine, which utilizes nanoparticles for cancer diagnosis and therapy by capitalizing on the increased surface area-to-volume ratio, the passive/active targeting ability and high loading capacity, the greater interaction cross section with biological tissues, the rich surface properties of nanomaterials, the facile decoration of nanomaterials with a plethora of functionalities, and the potential for multiplexing several functionalities within one construct. This review provides a comprehensive discussion of nuclear nanomedicine using tumor-targeted nanoparticles for cancer radiation therapy with either pre-embedded radionuclides or nonradioactive materials which can be extrinsically triggered using various external nuclear particle sources to produce in situ radioactivity. In addition, it describes the prospect of combining nuclear nanomedicine with other modalities to enable synergistically enhanced combination therapies. The review also discusses advances in the fabrication of radionuclides as well as describes laser ablation technologies for producing nanoradiopharmaceuticals, which combine the ease of production with exceptional purity and rapid biodegradability, along with additional imaging or therapeutic functionalities. From a practical standpoint, these attributes of nanoradiopharmaceuticals may provide distinct advantages in diagnostic/therapeutic sensitivity and specificity, imaging resolution, and scalability of turnkey platforms. Coupling image-guided targeted radiation therapy with the possibility of in situ activation of nanomaterials as well as combining with other therapeutic modalities using a multifunctional nanoplatform could herald an era of exciting technological and therapeutic advances to radically transform the landscape of nuclear medicine. The review concludes with a discussion of current challenges and presents the authors' views on future opportunities to stimulate further research in this rewarding field of high societal impact.

Long-term durability is critically important for the commercialization of perovskite solar cells (PSCs). The ionic character of the perovskite and the hydrophilicity of commonly used additives for the hole-transporting layer (HTL), such as lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) and tert -butylpyridine ( t BP), render PSCs prone to moisture attack, compromising their long-term stability. Here we introduce a trifluoromethylation strategy to overcome this drawback and to boost the PSC's solar to electric power conversion efficiency (PCE). We employ 4-(trifluoromethyl)benzylammonium iodide (TFMBAI) as an amphiphilic modifier for interfacial defect mitigation and 4-(trifluoromethyl)pyridine (TFP) as an additive to enhance the HTL's hydrophobicity. Surface treatment of the triple-cation perovskite with TFMBAI largely suppressed the nonradiative charge carrier recombination, boosting the PCE from 20.9% to 23.9% and suppressing hysteresis, while adding TFP to the HTL enhanced the PCS's resistance to moisture while maintaining its high PCE. Taking advantage of the synergistic effects resulting from the combination of both fluoromethylated modifiers, we realize TFMBAI/TFP-based highly efficient PSCs with excellent operational stability and resistance to moisture, retaining over 96% of their initial efficiency after 500 h maximum power point tracking (MPPT) under simulated 1 sun irradiation and 97% of their initial efficiency after 1100 h of exposure under ambient conditions to a relative humidity of 60-70%.

5-Ammonium valeric acid (AVA) is a frequently used additive in the preparation of lead halide perovskites. However, its microscopic role as passivating, cross-linking, or templating agent is far from clear. In this work, we provide density functional theory-based structural models for the Ruddlesden-Popper (RP) phases of AVA 2 (CH 3 NH 3 ) n-1 Pb n I 3 n+1 for n = 1, 2, and 3 and validate with experimental data on polycrystalline samples for n = 1. The structural and electronic properties of the AVA-based RP phases are compared to the ones of other linker families. In contrast to aromatic and aliphatic spacers without additional functional groups, the RP phases of AVA are characterized by the formation of a regular and stable H-bonding network between the carbonyl head groups of adjacent AVA molecules in opposite layers. Because of these additional interactions, the penetration depth of the organic layer into the perovskite sheet is reduced with direct consequences for its crystalline phase. The possibility of forming strong interlinker hydrogen bonds may lead to an enhanced thermal stability.

Electron transport layers (ETLs) with suitable energy level alignment for facilitating charge carrier transport as well as electron extraction are essential for planar heterojunction perovskite solar cells (PSCs) to achieve high open-circuit voltage ( V OC ) and short-circuit current. Herein we systematically investigate band offset between ETL and perovskite absorber by tuning F doping level in SnO 2 nanocrystal. We demonstrate that gradual substitution of F - into the SnO 2 ETL can effectively reduce the band offset and result in a substantial increase in device V OC . Consequently, a power conversion efficiency of 20.2% with V OC of 1.13 V can be achieved under AM 1.5 G illumination for planar heterojunction PSCs using F-doped SnO 2 bilayer ETL. Our finding provides a simple pathway to tailor ETL/perovskite band offset to increase built-in electric field of planar heterojunction PSCs for maximizing V OC and charge collection simultaneously.

Compositional engineering of a mixed cation/mixed halide perovskite in the form of (FAPbI 3 ) 0.85 (MAPbBr 3 ) 0.15 is one of the most effective strategies to obtain record-efficiency perovskite solar cells. However, the perovskite self-organization upon crystallization and the final elemental distribution, which are paramount for device optimization, are still poorly understood. Here we map the nanoscale charge carrier and elemental distribution of mixed perovskite films yielding 20% efficient devices. Combining a novel in-house-developed high-resolution helium ion microscope coupled with a secondary ion mass spectrometer (HIM-SIMS) with Kelvin probe force microscopy (KPFM), we demonstrate that part of the mixed perovskite film intrinsically segregates into iodide-rich perovskite nanodomains on a length scale of up to a few hundred nanometers. Thus, the homogeneity of the film is disrupted, leading to a variation in the optical properties at the micrometer scale. Our results provide unprecedented understanding of the nanoscale perovskite composition.

Amphiphilic sensitizers are central to the function of dye-sensitized solar cells. It is known that the cell's performance depends on the molecular arrangement and the density of the dye on the semiconductor surface, but a molecular-level picture of the cell-electrolyte interface is still lacking. Here, we present subnanometer in situ atomic force microscopy images of the Z907 dye at the surface of TiO2 in a relevant liquid. Our results reveal changes in the conformation and the lateral arrangement of the dye molecules, depending on their average packing density on the surface. Complementary quantitative measurements on the ensemble of the film are obtained by the quartz-crystal microbalance with dissipation technique. An atomistic picture of the dye coverage-dependent packing, the effectiveness of the hydrophobic alkyl chains as blocking layer, and the solvent accessibility is obtained from molecular dynamics simulations.

Alpha-Fe(2)O(3) films having a mesoscopic leaflet type structure were produced for the first time by ultrasonic spray pyrolysis (USP) to explore their potential as oxygen-evolving photoanodes. The target of these studies is to use translucent hematite films deposited on conducting fluorine doped tin oxide (FTO) glass as top electrodes in a tandem cell that accomplishes the cleavage of water into hydrogen and oxygen by sunlight. The properties of layers made by USP were compared to those deposited by conventional spray pyrolysis (SP). Although both types of films show similar XRD and UV-visible and Raman spectra, they differ greatly in their morphology. The mesoscopic alpha-Fe(2)O(3) layers produced by USP consist mainly of 100 nm-sized platelets with a thickness of 5-10 nm. These nanosheets are oriented mainly perpendicularly to the FTO support, their flat surface exposing (001) facets. The mesoscopic leaflet structure has the advantage that it allows for efficient harvesting of visible light, while offering at the same time the very short distance required for the photogenerated holes to reach the electrolyte interface before recombining with conduction band electrons. This allows for water oxidation by the valence band holes even though their diffusion length is only a few nanometers. Distances are longer in the particles produced by SP favoring recombination of photoinduced charge carriers. Open-circuit photovoltage measurements indicate a lower surface state density for the nanoplatelets as compared to the round particles. These factors explain the much higher photoactivity of the USP compared to the SP deposited alpha-Fe(2)O(3) layers. Addition of hydrogen peroxide to the alkaline electrolyte further improves the photocurrent-voltage characteristics of films generated by USP indicating the hole transfer from the valence band of the semiconductor oxide to the adsorbed water to be the rate-limiting kinetic step in the oxygen generation reaction.