Efficient remediation of different concentrations of Cr-contaminated soils by nano zero-valent iron modified with carboxymethyl cellulose and biochar.

Nano zero-valent iron (nZVI) is widely used in soil remediation due to its high reactivity. However, the easy agglomeration, poor antioxidant ability and passivation layer of Fe-Cr coprecipitates of nZVI have limited its application scale in Cr-contaminated soil remediation, especially in high concentration of Cr-contaminated soil. Herein, we found that the carboxymethyl cellulose on nZVI particles could increase the zeta potential value of soil and change the phase of nZVI. Along with the presence of biochar, 97.0% and 96.6% Cr immobilization efficiency through CMC-nZVI/BC were respectively achieved in high and low concentrations of Cr-contaminated soils after 90-days remediation. In addition, the immobilization efficiency of Cr(VI) only decreased by 5.1% through CMC-nZVI/BC treatment after 10 weeks aging in air, attributing to the strong antioxidation ability. As for the surrounding Cr-contaminated groundwater, the Cr(VI) removal capacity of CMC-nZVI/BC was evaluated under different reaction conditions through column experiments and COMSOL Multiphysics. CMC-nZVI/BC could efficiently remove 85% of Cr(VI) in about 400 hr when the initial Cr(VI) concentration was 40 mg/L and the flow rate was 0.5 mL/min. This study demonstrates that uniformly dispersed CMC-nZVI/BC has an excellent remediation effect on different concentrations of Cr-contaminated soils.

Resolving the interactions between hydrophilic CdTe quantum dots and positively charged membranes at the nanoscale.

The use of quantum dot nanoparticles (QDs) in bio-applications has gained quite some interest and requires a deep understanding of their interactions with model cell membranes. This involves assessing the extent of nanoparticle disruption of the membrane and how it depends on both nanoparticle and membrane physicochemical properties. Surface charge plays an important role in nanoparticle adsorption, which is primarily driven by electrostatic interactions; yet, once adsorbed, most reported works overlook the subsequent spatial nanoparticle insertion and location within the membrane. There is therefore a need for studies to assess the mutual role of membrane and nanoparticle charge into membrane structure and stability at the nanoscale, with a view to better design and control the functionality of these nanomaterials. In this work, we have resolved the extent of the interactions between hydrophilic, negatively charged CdTe QDs and positively charged lipid bilayers. A multiscale combination of surface-sensitive techniques enabled probing how surface charge mediates QD adsorption and membrane reorganization. Increasing membrane surface charge results into a larger adsorption of oppositely charged QDs, concomitantly inducing structural changes. Hydration of the membrane hydrophobic parts by QDs goes deeper into the inner leaflet with increasing membrane charge, resulting in supported lipid bilayers with decreased nanomechanical stability.

Relationships of ternary activities for the enhanced Cr(VI) removal by coupling nanoscale zerovalent iron with sulfidation and carboxymethyl cellulose.

Nanoscale zerovalent iron (nZVI) has been extensively applied in water pollution control. However, the reactivity of nZVI toward contaminants is mainly limited by its corrosion and agglomeration. In this study, the nZVI modified by sulfidation coupled with carboxymethyl cellulose (CMC) (C-S-nZVI) was synthesized and characterized by TEM and electrochemical techniques. Taking Cr(VI) as the contaminant, it was found that the sulfidation could couple with CMC modification to not only enhance the reactivity of nZVI toward Cr(VI), but also regulate the sedimentation activity and corrosion activity of nZVI in water. Particularly, the optimal kobs (0.0816 min-1) obtained by the C-S-nZVIone-0.16 (i.e., one-step sulfidation and its S/Fe molar ratio was 0.16) was approximately 27.2 times higher than that by the nZVI (0.0030 min-1). Moreover, based on the correlation analysis of the ternary activities, this study confirmed that the reactivity of C-S-nZVI toward Cr(VI) was negatively correlated with its sedimentation activity (slope=-0.7623, R=0.59) and corrosion activity (slope=-0.0171, R=0.56), respectively. XPS and TEM results further revealed that CMC could couple with iron sulfides (FeSx) to enhance the mass transfer of Cr(VI) toward nZVI and subsequent electron transfer from Fe0 core to out, ultimately improving the reduction of Cr(VI) by nZVI. Overall, this study introduced a new evaluation method based on the ternary activity of nZVI, providing theoretical support for the practical application of nZVI-based technology.

Experimental Determination of the Chiral and Achiral Shape Diagrams of Tellurium Nanocrystals.

The interface between chirality and crystallization and mechanisms by which chirality propagates from crystal structure to overall shapes of crystals are a key topic in crystallography and stereochemistry. Recently, nanocrystals attracted attention as useful model systems for this kind of studies. Specifically, tellurium nanocrystals have been used to address questions on relations between chirality of the crystal structure and that of the overall shape. Previous studies of this system did not offer a comprehensive shape diagram and did not survey all the factors that determine whether shapes that form are chiral or not. In the current report, the distribution of chiral and achiral shapes in this system as a function of different physical and chemical parameters is determined experimentally. It is shown that there is a common logic for formation of chiral shapes, that is, growth at conditions that favor the growth of more reactive nuclei. The experiments also reveal more morphologies than previously encountered, suggesting that a systematic change of conditions in nanocrystal growth is key for identifying morphologies that exist only in a narrow range of conditions.

Factors to consider before choosing EV labeling method for fluorescence-based techniques.

A well-designed fluorescence-based analysis of extracellular vesicles (EV) can provide insights into the size, morphology, and biological function of EVs, which can be used in medical applications. Fluorescent nanoparticle tracking analysis with appropriate controls can provide reliable data for size and concentration measurements, while nanoscale flow cytometry is the most appropriate tool for characterizing molecular cargoes. Label selection is a crucial element in all fluorescence methods. The most comprehensive data can be obtained if several labeling approaches for a given marker are used, as they would provide complementary information about EV populations and interactions with the cells. In all EV-related experiments, the influence of lipoproteins and protein corona on the results should be considered. By reviewing and considering all the factors affecting EV labeling methods used in fluorescence-based techniques, we can assert that the data will provide as accurate as possible information about true EV biology and offer precise, clinically applicable information for future EV-based diagnostic or therapeutic applications.

Stimulation of fracture mineralization by salt-inducible kinase inhibitors.

Introduction: Over 6.8 million fractures occur annually in the US, with 10% experiencing delayed- or non-union. Anabolic therapeutics like PTH analogs stimulate fracture repair, and small molecule salt inducible kinase (SIK) inhibitors mimic PTH action. This study tests whether the SIK inhibitor YKL-05-099 accelerates fracture callus osteogenesis. Methods: 126 female mice underwent femoral shaft pinning and midshaft fracture, receiving daily injections of PBS, YKL-05-099, or PTH. Callus tissues were analyzed via RT-qPCR, histology, single-cell RNA-seq, and µCT imaging. Biomechanical testing evaluated tissue rigidity. A hydrogel-based delivery system for PTH and siRNAs targeting SIK2/SIK3 was developed and tested. Results: YKL-05-099 and PTH-treated mice showed higher mineralized callus volume fraction and improved structural rigidity. RNA-seq indicated YKL-05-099 increased osteoblast subsets and reduced chondrocyte precursors. Hydrogel-released siRNAs maintained target knockdown, accelerating callus mineralization. Discussion: YKL-05-099 enhances fracture repair, supporting selective SIK inhibitors' development for clinical use. Hydrogel-based siRNA delivery offers targeted localized treatment at fracture sites.

Chiral Symmetry Breaking in Colloidal Metal Nanoparticle Solutions by Circularly Polarized Light.

Shape symmetry breaking in the formation of inorganic nanostructures is of significant current interest. It was typically achieved through the growth of colloidal nanoparticles with adsorbed chiral molecules. Photochemical processes induced through asymmetric plasmon excitation by circularly polarized light in surface immobilized nanostructures also led to symmetry breaking. Here, we show that chiral symmetry breaking can be achieved by randomly rotating gold@silver core-shell nanobars in colloidal solution using circularly polarized illumination, where orientational averaging does not eliminate the symmetry breaking of an asymmetric plasmon-induced galvanic replacement reaction. Different morphological effects that are produced by circularly vs linearly polarized light illumination demonstrate the intricate effect of light polarization on the localized plasmonic-induced photochemical response. The essential features of this symmetry breaking, such as illumination wavelength dependence, were reproduced by simulations of circularly polarized light-excited-plasmon-induced hot-electron generation as the source for asymmetric metal deposition. The symmetry breaking becomes smaller in more symmetric geometrical shapes, such as triangular nanoprisms and nanocubes, and down to zero in spherical ones. The degree of symmetry breaking rises when the nanobars are immobilized on a substrate and illuminated from a single direction.

A nanoscale natural drug delivery system for targeted drug delivery against ovarian cancer: action mechanism, application enlightenment and future potential.

Ovarian cancer (OC) is one of the deadliest gynecological malignancies in the world and is the leading cause of cancer-related death in women. The complexity and difficult-to-treat nature of OC pose a huge challenge to the treatment of the disease, Therefore, it is critical to find green and sustainable drug treatment options. Natural drugs have wide sources, many targets, and high safety, and are currently recognized as ideal drugs for tumor treatment, has previously been found to have a good effect on controlling tumor progression and reducing the burden of metastasis. However, its clinical transformation is often hindered by structural stability, bioavailability, and bioactivity. Emerging technologies for the treatment of OC, such as photodynamic therapy, immunotherapy, targeted therapy, gene therapy, molecular therapy, and nanotherapy, are developing rapidly, particularly, nanotechnology can play a bridging role between different therapies, synergistically drive the complementary role of differentiated treatment schemes, and has a wide range of clinical application prospects. In this review, nanoscale natural drug delivery systems (NNDDS) for targeted drug delivery against OC were extensively explored. We reviewed the mechanism of action of natural drugs against OC, reviewed the morphological composition and delivery potential of drug nanocarriers based on the application of nanotechnology in the treatment of OC, and discussed the limitations of current NNDDS research. After elucidating these problems, it will provide a theoretical basis for future exploration of novel NNDDS for anti-OC therapy.

Coordinate-based simulation of pair distance distribution functions for small and large molecular assemblies: implementation and applications.

X-ray scattering has become a major tool in the structural characterization of nanoscale materials. Thanks to the widely available experimental and computational atomic models, coordinate-based X-ray scattering simulation has played a crucial role in data interpretation in the past two decades. However, simulation of real-space pair distance distribution functions (PDDFs) from small- and wide-angle X-ray scattering, SAXS/WAXS, has been relatively less exploited. This study presents a comparison of PDDF simulation methods, which are applied to molecular structures that range in size from ß-cyclo-dextrin [1 kDa molecular weight (MW), 66 non-hydrogen atoms] to the satellite tobacco mosaic virus capsid (1.1 MDa MW, 81 960 non-hydrogen atoms). The results demonstrate the power of interpretation of experimental SAXS/WAXS from the real-space view, particularly by providing a more intuitive method for understanding of partial structure contributions. Furthermore, the computational efficiency of PDDF simulation algorithms makes them attractive as approaches for the analysis of large nanoscale materials and biological assemblies. The simulation methods demonstrated in this article have been implemented in stand-alone software, SolX 3.0, which is available to download from https://12idb.xray.aps.anl.gov/solx.html.

Insights into the Biological Activity and Bio-Interaction Properties of Nanoscale Imine-Based 2D and 3D Covalent Organic Frameworks.

Covalent Organic Frameworks (COFs) emerged as versatile materials with promising potential in  biomedicine. Their customizable functionalities and tunable pore structures make them valuable for various biomedical applications such as biosensing, bioimaging, antimicrobial activity, and targeted drug delivery. Despite efforts made to create nanoscale COFs (nCOFs) to enhance their interaction with biological systems, a comprehensive understanding of their inherent biological activities remains a significant challenge. In this study, a thorough investigation is conducted into the biocompatibility and anti-neoplastic properties of two distinct imine-based nCOFs. The approach involved an in-depth analysis of these nCOFs through in vitro experiments with various cell types and in vivo assessments using murine models. These findings revealed significant cytotoxic effects on tumor cells. Moreover, the activation of multiple cellular death pathways, including apoptosis, necroptosis, and ferroptosis is determined, supported by evidence at the molecular level. In vivo evaluations exhibited marked inhibition of tumor growth, associated with the elevated spontaneous accumulation of nCOFs in tumor tissues and the modulation of cell death-related protein expression. The research contributes to developing a roadmap for the characterization of the intricate interactions between nCOFs and biological systems and opens new avenues for exploiting their therapeutic potential in advanced biomedical applications.

Ultralow Contact Thermal Resistance between Bismuth Selenide Nanoribbons Achieved by Current-Induced Annealing.

Thermal resistance at interfaces/contacts stands as a persistent and increasingly critical issue, which hinders ultimate scaling and the performance of electronic devices. Compared to the extensive research on contact electrical resistance, contact thermal resistance and its mitigation strategies have received relatively less attention. Here, we report on an effective, in situ, and energy-efficient approach for enhancing thermal transport through the contact between semiconducting nanoribbons. By applying microampere-level electrical currents to the contact between Bi2Se3 nanoribbons, we demonstrate that the contact thermal resistance between two nanoribbon segments is reduced dramatically by a factor of 4, rendering the total thermal resistance of two ribbon segments with a contact approximately the same as that of the corresponding single continuous nanoribbon of the same length. Analysis suggests that the ultralow contact thermal resistance is due to enhanced phonon transmission as a result of enhanced adhesion energy at the contact, with marginal contributions from direct electron-phonon coupling, even for ohmic contacts. Our work introduces a broadly applicable electrical treatment approach to various contacts between conducting and semiconducting materials, which has important implications for the design and operation of nanoelectronic devices and energy converters.

Domain Dynamics Response to Polarization Switching in Relaxor Ferroelectrics.

Nanoscale polar regions, or nanodomains (NDs), are crucial for understanding the domain structure and high susceptibility of relaxors. However, unveiling the evolution and function of NDs during polarization switching at the microscopic level is of great challenge. The experimental in situ characterization of NDs under electric-field perturbations, and computational accurate prediction of the dipole switching within a sufficiently large supercell, are notoriously tricky and tedious. These difficulties hinder a full understanding of the link between micro domain dynamics and macro polarization switching. Herein, the real-time evolution of NDs at the nanoscale is observed and visualized during polarization switching in an exemplary relaxor system of Bi5- xLaxMg0.5Ti3.5O15. Two fundamentally different domain switching pathways and dynamic characteristics are revealed: one steep, bipolar-like switching between two degenerate polarization states; and another flat, multi-step switching process with a thermodynamically stable non-polar mesophase mediating the degenerate polarization states. The two are determined by the distinct Landau energy landscapes that are strongly dependent on the intrinsic domain configurations and interdomain interactions. This work bridges the gap between micro domain dynamics and macro polarization switching, providing a guiding principle for the strategic design and optimization of relaxors.

[Research progress of nanoscale zero-valent iron in synergistic combinations of denitrifying bacteria for nitrate removal].

Nitrate (NO3--N) is a common inorganic nitrogen pollutant in water. Excessive NO3--N can lead to water eutrophication and threaten human health. Nanoscale zero-valent iron (nZVI) has attracted much attention in NO3--N removal due to its high specific surface and excellent electron donor properties. The combination of nZVI and denitrifying bacteria (DNB) demonstrates high efficiency in converting NO3--N into N2. This approach not only substantially enhances the removal rate of NO3--N but also exhibits superior environmental sustainability compared with conventional chemical denitrification methods. Accordingly, it holds substantial promise for mitigating NO3--N pollution and warrants further exploration in the pollution control. Therefore, it is necessary to understand the interaction mechanism between nZVI and DNB for NO3--N removal. This paper details the factors affecting the removal of NO3--N by nZVI combined with DNB, reviews the latest research progress in this field, elaborates on the interaction mechanism between nZVI and DNB for NO3--N removal, and discusses the challenges and future research directions of NO3--N removal by nZVI combined with DNB. This review aims to provide a theoretical basis for the development of efficient approaches for the remediation of NO3--N pollution.

A Nonlinear Peptide Topology for Synthetic Virions.

a nonlinear de novo peptide topology for the assembly of synthetic virions is reported. The topology is a backbone cyclized amino-acid sequence in which polar l- and hydrophobic d-amino acid residues of the same-type alternate. This arrangement introduces pseudo C4 symmetries of side chains within the same cyclopeptide ring, allowing for the lateral propagation of cyclopeptides into networks with a [3/6, 4]-fold rotational symmetry closing into virus-like shells. A combination of computational and experimental approaches was used to establish that the topology forms morphologically uniform, nonaggregating and nontoxic nanoscale shells. These effectively encapsulate genetic cargo and promote its intracellular delivery and a target genetic response. The design introduces a nanotechnology inspired solution for engineering virus-like systems thereby expanding traditional molecular biology approaches used to create artificial biology to chemical space.

Observing the crack tip behavior at the nanoscale during fracture of ceramics.

Ultimately, brittle fracture involves breaking atomic bonds. However, we still lack a clear picture of what happens in the highly deformed region around a moving crack tip. Consequently, we still cannot link nanoscale phenomena with the macroscopic toughness of materials. The unsolved challenge is to observe the movement of the crack front at the nanoscale while extracting quantitative information. Here, we address this challenge by monitoring stable crack growth inside a transmission electron microscope. Our analysis demonstrates how phase transformation toughening, previously thought to be effective at the microscale and above, promotes crack deflection at the nanolevel and increases the fracture resistance. The work is a first step to help connecting the atomistic and continuous view of fracture in a way that can guide the design of the next generation of strong and tough materials demanded by technologies as diverse as healthcare, energy generation, or transport.

Probing Nanoscale Charge Transport Mechanisms in Quasi-2D Halide Perovskites for Photovoltaic Applications.

Quasi-2D layered halide perovskites (quasi-2DLPs) have emerged as promising materials for photovoltaic (PV) applications owing to their advantageous bandgap for absorbing visible light and the improved stability they enable. Their charge transport mechanism is heavily influenced by the grain orientation of their crystals as well as their nanostructures, such as grain boundaries (GBs) and edge states─the formation of which is inevitable in polycrystalline quasi-2DLP thin films. Despite their importance, the impact of these features on charge transport remains unexplored. In this study, we conduct a detailed investigation on polycrystalline quasi-2DLP thin films and devices, carefully analyzing how grain orientation and nanostructures influence charge transport. Employing nondestructive atomic force microscopy (AFM) topography, along with transient absorption spectroscopy (TAS) and grazing-incidence wide-angle X-ray scattering (GIWAXS), we obtained significant insights regarding the phase purity, crystallographic information, and morphologies of these films. Moreover, our systematic investigation using AFM-based techniques, including Kelvin probe force microscopy (KPFM) and conductive AFM (c-AFM), elucidates the roles played by GBs and edge states in shaping charge transport behavior. In particular, the local band structure along the GBs and edge states within both vertical and parallel grains was found to selectively repel electrons and holes, thus facilitating charge carrier separation. These findings provide perspectives for the development of high-performance quasi-2DLP PV devices and highlight potential approaches that can leverage the intrinsic properties of quasi-2DLPs to advance the performance of perovskite solar cells.

The Xaliproden Nanoscale Zirconium-Porphyrin Metal-Organic Framework (XAL-NPMOF) Promotes Photoreceptor Regeneration Following Oxidative and Inflammatory Insults.

Background: Age-related macular degeneration (AMD) is becoming the leading cause of blindness in the aged population. The death of photoreceptors is the principal event which is lack of curative treatment. Xaliproden, a highly selective synthetic 5-OH-tryptamine (5HT) 1A receptor agonist, has the neuroprotective potential. However, its application has been limited by the insoluble formulation, low utilization efficiency and side effects caused by systemic administration. Methods: Nanoscale zirconium-porphyrin metal-organic framework (NPMOF) was used as a skeleton and loaded with xaliproden (XAL) to prepare a novel kind of nanoparticle, namely, XAL-NPMOF. The human umbilical vein endothelial cells, zebrafish embryos and larvae were used to test the biotoxicity and fluorescence imaging capability of XAL-NPMOF both in vitro and in vivo. A photoreceptor degeneration model was generated by intense light injury in adult zebrafish and XAL-NPMOF was delivered to the injured retina by intraocular injection. The photoreceptor regeneration, inflammatory response and visual function were explored by immunohistochemistry, quantitative real-time polymerase chain reaction and optomotor response analysis. Results: Following a single XAL-NPMOF intraocular injection, the injured retina underwent the faster photoreceptor regeneration with a recovery of visual function via promoting cell proliferation, suppressing the inflammatory responses and increasing the expression of antioxidases. Conclusion: As an amplifier, NPMOF can enhance the anti-inflammatory efficacy and neuroprotective effect of xaliproden. XAL-NPMOF could be a novel and convenient option for the treatment of AMD.

Multiplex antimicrobial activities of the self-assembled amphiphilic polypeptide ß nanofiber KF-5 against vaginal pathogens.

BACKGROUND: Vaginal infections caused by multidrug-resistant pathogens such as Candida albicans and Gardnerella spp. represent a significant health challenge. Current treatments often fail because of resistance and toxicity. This study aimed to synthesize and characterize a novel amphiphilic polypeptide, KF-5, and evaluate its antibacterial and antifungal activities, biocompatibility, and potential mechanisms of action. RESULTS: The KF-5 peptide was synthesized via solid-phase peptide synthesis and self-assembled into nanostructures with filamentous and hydrogel-like configurations. Characterization by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM) confirmed the unique nanostructural properties of KF-5. KF-5 (125, 250, or 500 µg/ml) demonstrated potent antibacterial and antifungal activities, with significant inhibitory effects on drug-resistant Candida albicans and Gardnerella spp. (P < 0.05). In vitro assays revealed that 500 µg/ml KF-5 disrupted microbial cell membranes, increased membrane permeability, and induced lipid oxidation, leading to cell death (P < 0.05). Cytotoxicity tests revealed minimal toxicity in human vaginal epithelial cells, keratinocytes, and macrophages, with over 95% viability at high concentrations. Molecular dynamics simulations indicated that KF-5 interacts with phospholipid bilayers through electrostatic interactions, causing membrane disruption. In vivo studies using a mouse model of vaginal infection revealed that 0.5, 1, and 2 mg/ml KF-5 significantly reduced fungal burden and inflammation, and histological analysis confirmed the restoration of vaginal mucosal integrity (P < 0.01). Compared with conventional antifungal treatments such as miconazole, KF-5 exhibited superior efficacy (P < 0.01). CONCLUSIONS: KF-5 demonstrates significant potential as a safe and effective antimicrobial agent for treating vaginal infections. Its ability to disrupt microbial membranes while maintaining biocompatibility with human cells highlights its potential for clinical application. These findings provide a foundation for further development of KF-5 as a therapeutic option for combating drug-resistant infections.

Emerging Chirality and Moiré Dynamics in Twisted Layered Material Heterostructures.

Moiré superstructures arising at twisted 2D interfaces have recently attracted the attention of the scientific community due to exotic quantum states and unique mechanical and tribological behaviors that they exhibit. Here, we predict the emergence of chiral distortions in twisted layered interfaces of finite dimensions. This phenomenon originates in intricate interplay between interfacial interactions and contact boundary constraints. A metric termed the fractional chiral area is introduced to quantify the overall chirality of the moiré superstructure and to characterize its spatial distribution. Despite the equilibrium nature of the discovered energetic and structural chirality effects, they are shown to be manifested in the twisting dynamics of layered interfaces, which demonstrates a continuous transition from stick-slip to smooth rotation with no external trigger.

Time Crystals from Single-Molecule Magnet Arrays.

Time crystals, a unique nonequilibrium quantum phenomenon with promising applications in current quantum technologies, mark a significant advance in quantum mechanics. Although traditionally studied in atom-cavity and optical lattice systems, pursuing alternative nanoscale platforms for time crystals is crucial. Here we theoretically predict discrete time crystals in a periodically driven molecular magnet array, modeled by a spin-S Heisenberg Hamiltonian with significant quadratic anisotropy, taken with realistic and experimentally relevant physical parameters. Surprisingly, we find that the time crystal response frequency correlates with the energy levels of the individual magnets and is essentially independent of the exchange coupling. The latter is unexpectedly manifested through a pulse-like oscillation in the magnetization envelope, signaling a many-body response. These results show that molecular magnets can be a rich platform for studying time-crystalline behavior and possibly other out-of-equilibrium quantum many-body dynamics.