Dual-mode harvest solar energy for photothermal Cu2-xSe biomineralization and seawater desalination by biotic-abiotic hybrid.

Biotic-abiotic hybrid photocatalytic system is an innovative strategy to capture solar energy. Diversifying solar energy conversion products and balancing photoelectron generation and transduction are critical to unravel the potential of hybrid photocatalysis. Here, we harvest solar energy in a dual mode for Cu2-xSe nanoparticles biomineralization and seawater desalination by integrating the merits of Shewanella oneidensis MR-1 and biogenic nanoparticles. Photoelectrons generated by extracellular Se0 nanoparticles power Cu2-xSe synthesis through two pathways that either cross the outer membrane to activate periplasmic Cu(II) reduction or are directly delivered into the extracellular space for Cu(I) evolution. Meanwhile, photoelectrons drive periplasmic Cu(II) reduction by reversing MtrABC complexes in S. oneidensis. Moreover, the unique photothermal feature of the as-prepared Cu2-xSe nanoparticles, the natural hydrophilicity, and the linking properties of bacterium offer a convenient way to tailor photothermal membranes for solar water production. This study provides a paradigm for balancing the source and sink of photoelectrons and diversifying solar energy conversion products in biotic-abiotic hybrid platforms.

Detection of early pulmonary emphysema by multi-contrast x-ray Talbot-Lau interferometer.

BACKGROUND: Pulmonary emphysema is a part of chronic obstructive pulmonary disease, which is an irreversible chronic respiratory disease. In order to avoid further damage to lung tissue, early diagnosis and treatment of pulmonary emphysema is essential. PURPOSE: Early pulmonary emphysema diagnosis is difficult with conventional radiographic imaging. Recently, x-ray phase contrast imaging has proved to be an effective and promising imaging strategy for soft tissue, due to its high sensitivity and multi-contrast. The aim of this study is to diagnose pulmonary emphysema early utilizing an x-ray Talbot-Lau interferometer (TLI). METHODS: We successfully established the mouse model of emphysema by porcine pancreatic elastase treatment, and then used the established x-ray TLI to perform imaging experiments on the mice with different treatment time. The traditional absorption CT and phase contrast CT were obtained simultaneously through TLI. The CT results and histopathology of mice lung in different treatment time were quantitatively analyzed. RESULTS: By imaging mice lungs, it can be found that phase contrast has higher sensitivity than absorption contrast in early pulmonary emphysema. The results show that the phase contrast signal could distinguish the pulmonary emphysema earlier than the conventional attenuation signal, which can be consistent with histological images. Through the quantitative analysis of pathological section and phase contrast CT, it can be found that there is a strong linear correlation. CONCLUSIONS: In this study, we quantitatively analyze mean linear intercept of histological sections and CT values of mice. The results show that the phase contrast signal has higher imaging sensitivity than the attenuation signal. X-ray TLI multi-contrast imaging is proved as a potential diagnostic method for early pulmonary emphysema in mice.

Near-Native Imaging of Label-Free Silver Nanoparticles-Triggered 3D Subcellular Ultrastructural Reorganization in Microalgae.

Understanding the spatial orientation of nanoparticles and the corresponding subcellular architecture events favors uncovering fundamental toxic mechanisms and predicting response pathways of organisms toward environmental stressors. Herein, we map the spatial location of label-free citrate-coated Ag nanoparticles (Cit-AgNPs) and the corresponding subcellular reorganization in microalgae by a noninvasive 3D imaging approach, cryo-soft X-ray tomography (cryo-SXT). Cryo-SXT near-natively displays the 3D maps of Cit-AgNPs presenting in rarely identified sites, namely, extracellular polymeric substances (EPS) and the cytoplasm. By comparative 3D morphological assay, we observe that Cit-AgNPs disrupt the cellular ultrastructural homeostasis, triggering a severe malformation of cytoplasmic organelles with energy-producing and stress-regulating functions. AgNPs exposure causes evident disruption of the chloroplast membrane, significant attenuation of the pyrenoid matrix and starch sheath, extreme swelling of starch granules and lipid droplets, and shrinkage of the nucleolus. In accompaniment, the number and volume occupancy of starch granules are significantly increased. Meanwhile, the spatial topology of starch granules extends from the chloroplast to the cytoplasm with a dispersed distribution. Linking the dynamics of the internal structure and the alteration of physiological properties, we derive a comprehensive cytotoxic and response pathway of microalgae exposed to AgNPs. This work provides a perspective for assessing the toxicity at subcellular scales to achieve label-free nanoparticle-caused ultrastructure remodeling of phytoplankton.

High energy x-ray Talbot-Lau interferometer employing a microarray anode-structured target source to extend the field of view.

Objective. High energy and large field of view (FOV) phase contrast imaging is crucial for biological and even medical applications. Although some works have devoted to achieving a large FOV at high energy through bending gratings and so on, which would be extremely challenging in medical high energy imaging.Approach.We analyze the angular shadowing effect of planar gratings in high-energy x-ray Talbot-Lau interferometer (XTLI). Then we design and develop an inverse XTLI coupled with a microarray anode-structured target source to extend the FOV at high energy.Main results.Our experimental results demonstrate the benefit of the source in the inverse XTLI and a large FOV of 106.6 mm in the horizontal direction is achieved at 40 keV. Based on this system, experiments of a mouse demonstrate the potential advantage of phase contrast mode in imaging lung tissue.Significance.We extend the FOV in a compact XTLI using a microarray anode-structured target source coupled with an inverse geometry, which eliminates grating G0 and relaxes the fabrication difficulty of G2. We believe the established design idea and imaging system would facilitate the wide applications of XTLI in high energy phase contrast imaging.

Direct Visualization and Restoration of Metallic Ion-Induced Subcellular Ultrastructural Remodeling.

Analysis of cellular ultrastructure dynamics and metal ions' fate can provide insights into the interaction between living organisms and metal ions. Here, we directly visualize the distribution of biogenic metallic aggregates, ion-induced subcellular reorganization, and the corresponding regulation effect in yeast by the near-native 3D imaging approach, cryo-soft X-ray tomography (cryo-SXT). By comparative 3D morphometric assessment, we observe the gold ions disrupting cellular organelle homeostasis, resulting in noticeable distortion and folding of vacuoles, apparent fragmentation of mitochondria, extreme swelling of lipid droplets, and formation of vesicles. The reconstructed 3D architecture of treated yeast demonstrates ∼65% of Au-rich sites in the periplasm, a comprehensive quantitative assessment unobtained by TEM. We also observe some AuNPs in rarely identified subcellular sites, namely, mitochondria and vesicles. Interestingly, the amount of gold deposition is positively correlated with the volume of lipid droplets. Shifting the external starting pH to near-neutral results in the reversion of changes in organelle architectures, boosting the amount of biogenic Au nanoparticles, and increasing cell viability. This study provides a strategy to analyze the metal ions-living organism interaction from subcellular architecture and spatial localization perspectives.

Simulation and Experimental Validation of a Pressurized Filling Method for Neutron Absorption Grating.

The absorption grating is a critical component of neutron phase contrast imaging technology, and its quality directly influences the sensitivity of the imaging system. Gadolinium (Gd) is a preferred neutron absorption material due to its high absorption coefficient, but its use in micro-nanofabrication poses significant challenges. In this study, we employed the particle filling method to fabricate neutron absorption gratings, and a pressurized filling method was introduced to enhance the filling rate. The filling rate was determined by the pressure on the surface of the particles, and the results demonstrate that the pressurized filling method can significantly increase the filling rate. Meanwhile, we investigated the effects of different pressures, groove widths, and Young's modulus of the material on the particle filling rate through simulations. The results indicate that higher pressure and wider grating grooves lead to a significant increase in particle filling rate, and the pressurized filling method can be utilized to fabricate large-size grating and produce uniformly filled absorption gratings. To further improve the efficiency of the pressurized filling method, we proposed a process optimization approach, resulting in a significant improvement in the fabrication efficiency.

On-Line Fluorescence Microscopy for Identification and Imaging of Apoptotic Cell with Synchrotron-Based Soft X-ray Tomography.

Synchrotron-based soft X-ray tomography (SXT), providing three-dimensional morphology and quantitative distribution of linear absorption coefficient (LAC) of the imaged objects, is widely used in many fields to obtain ultra-structure images, especially in cellular imaging. Off-line fluorescence microscopies (FMs) are combined to identify the type of organelles and status of cells. However, deformation and displacement usually occur during the transfer and loading process, which decreases the precision of two-modal images' registration. In this paper, we report on an on-line FM, at the SXT station (BL07W) of the National Synchrotron Radiation Laboratory (NSRL), which avoids deformation and displacement. Therefore, researchers can easily find the sample and take the useful data without tedious post-processing. Combining SXT with on-line FM, we achieved the identification and high-resolution imaging of an apoptotic cell. The experiments revealed that the LAC of the nucleus of the apoptotic cell was larger than that of a normal cell, which could be explained by nucleus pyknosis of the apoptotic cell.

A Magnesium/Lithium Hybrid-Ion Battery with Modified All-Phenyl-Complex-Based Electrolyte Displaying Ultralong Cycle Life and Ultrahigh Energy Density.

Magnesium/lithium hybrid-ion batteries (MLHBs) combine the advantages of high safety and fast ionic kinetics, which enable them to be promising emerging energy-storage systems. Here, a high-performance MLHB using a modified all-phenyl complex with a lithium bis(trifluoromethanesulfonyl)imide electrolyte and a NiCo2S4 cathode on a copper current collector is developed. A reversible conversion involving a copper collector with NiCo2S4 efficiently avoids the electrolyte dissociation and diffusion difficulties of Mg2+ ions, enabling low polarization and fast redox, which is verified by X-ray absorption near edge structure analysis. Such combination affords the best MLHB among all those ever reported, with a reversible capacity of 204.7 mAh g-1 after 2600 cycles at 2.0 A g-1, and delivers an ultrahigh full electrode-basis energy density of 708 Wh kg-1. The developed MLHB also achieves good rate performance and temperature tolerance at -10 and 50 °C with a low electrolyte consumption. The hybrid-ion battery system presented here could inspire a broad set of engineering potentials for high-safety battery technologies and beyond.

A Lamellar Yolk-Shell Lithium-Sulfur Battery Cathode Displaying Ultralong Cycling Life, High Rate Performance, and Temperature Tolerance.

The shuttling behavior and slow conversion kinetics of the intermediate lithium polysulfides are the severe obstacles for the application of lithium-sulfur (Li-S) batteries over a wide temperature range. Here, an engineered lamellar yolk-shell structure of In2 O3 @void@carbon for the Li-S battery cathode is developed for the first time to construct a powerful barrier that effectively inhibits the shuttling of polysulfides. On the basis of the unique nanochannel-containing morphology, the continuous kinetic transformation of sulfur and polysulfides is confined in a stable framework, which is demonstrated by using X-ray nanotomography. The constructed Li-S battery exhibits a high cycling capability over 1000 cycles at 1.0 C with a capacity decay rate as low as 0.038% per cycle, good rate performance, and temperature tolerance at -10, 25, and 50 °C. A nondestructive in situ monitoring method of the interfacial reaction resistance in different cycling stages is proposed, which provides a new analysis perspective for the development of emerging electrochemical energy-storage systems.

Regulating the synthesis rate and yield of bio-assembled FeS nanoparticles for efficient cancer therapy.

Biosynthesis has gained growing interest due to its energy efficiency and environmentally benign nature. Recently, biogenic iron sulfide nanoparticles (FeS NPs) have exhibited excellent performance in environmental remediation and energy recovery applications. However, their biosynthesis regulation strategy and application prospects in the biomedical field remain to be explored. Herein, biogenic FeS NPs are controllably synthesized by Shewanella oneidensis MR-1 and applied for cancer therapy. Tuning the synthesis rate and yield of biogenic FeS NPs is realized by altering the initial iron precursor dosage. Notably, increasing the precursor concentration decreases and delays FeS NP biosynthesis. The biogenic FeS NPs (30 nm) are homogeneously anchored on the cell surface of S. oneidensis MR-1. Moreover, the good hydrophilic nature and outstanding Fenton properties of the as-prepared FeS NPs endow them with good cancer therapy performance. The intracellular location of the FeS NPs taken up is visualized with a soft X-ray microscope (SXM). Highly efficient cancer cell killing can be achieved at extremely low concentrations (<12 µg mL-1), lower than those in reported works. Such good performance is attributed to the Fe2+ release, elevated ROS, reduced glutathione (GSH) consumption, and lipid hydroperoxide (LPO) generation. The resulting FeS NPs show excellent in vivo therapeutic performance. This work provides a facile, eco-friendly, and scalable approach to produce nanomedicine, demonstrating the potential of biogenic nanoparticles for use in cancer therapy.

Electric-field-assisted non-volatile magnetic switching in a magnetoelectronic hybrid structure.

Electric-field (E-field) control of magnetic switching provides an energy-efficient means to toggle the magnetic states in spintronic devices. The angular tunneling magnetoresistance (TMR) of an magnetic tunnel junction (MTJ)/PMN-PT magnetoelectronic hybrid indicates that the angle-dependent switching fields of the free layer can decrease significantly subject to the application of an E-field. In particular, the switching field along the major axis is reduced by 59% from 28.0 to 11.5 Oe as the E-field increases from 0 to 6 kV/cm, while the TMR ratio remains intact. The switching boundary angle decreases (increases) for the parallel (antiparallel) to antiparallel (parallel) state switch, resulting in a shrunk switching window size. The non-volatile and reversible 180° magnetization switching is demonstrated by using E-fields with a smaller magnetic field bias as low as 11.5 Oe. The angular magnetic switching originates from competition among the E-field-induced magnetoelastic anisotropy, magnetic shape anisotropy, and Zeeman energy, which is confirmed by micromagnetic simulations.

Generalized reverse projection method for grating-based phase tomography.

The reverse projection protocol results in fast phase-contrast imaging thanks to its compatibility with conventional computed-tomography scanning. Many researchers have proposed variants. However, all these reverse projection methods in grating-based phase-contrast imaging are built on the hypothesis of the synchronous phase of reference shifting curves in the whole field of view. The hypothesis imposes uniformity and alignment requirements on the gratings, thus the field of view is generally limited. In this paper, a generalized reverse projection method is presented analytically for the case of non-uniform reference in grating-based phase tomography. The method is demonstrated by theoretical derivation, numerical simulations and synchrotron radiation experiments. The influence of imaging position to sensitivity, and the phase-wrapping phenomenon are also discussed. The proposed method combines the advantages of the high efficiency of the reverse projection method and the universal applicability of the phase-stepping method. The authors believe that the method would be used widely in fast and dose-constrained imaging.

Fabricating 3D Metastructures by Simultaneous Modulation of Flexible Resist Stencils and Basal Molds.

Metamaterials have gained much attention thanks to their extraordinary and intriguing optical properties beyond natural materials. However, universal high-resolution fabrications of 3D micro/nanometastructures with high-resolution remain a challenge. Here, a novel approach to fabricate sophisticated 3D micro/nanostructures with excellent robustness and precise controllability is demonstrated by simultaneously modulating of flexible resist stencils and basal molds. This method allows arbitrary manipulations of morphology, size, and orientation, as well as contact angles of the objects. Combined with a new alignment strategy of high-resolution, previously inaccessible architectures are fabricated with ultrahigh precision, leading to an excellent spectra response from the fabricated metastructures. This method provides a new possibility to realize true 3D metamaterial fabrications featuring high-resolution and direct-compatibility with broad planar lithography platforms.

Quantifying redox heterogeneity in single-crystalline LiCoO2 cathode particles.

Active cathode particles are fundamental architectural units for the composite electrode of Li-ion batteries. The microstructure of the particles has a profound impact on their behavior and, consequently, on the cell-level electrochemical performance. LiCoO2 (LCO, a dominant cathode material) is often in the form of well-shaped particles, a few micrometres in size, with good crystallinity. In contrast to secondary particles (an agglomeration of many fine primary grains), which are the other common form of battery particles populated with structural and chemical defects, it is often anticipated that good particle crystallinity leads to superior mechanical robustness and suppressed charge heterogeneity. Yet, sub-particle level charge inhomogeneity in LCO particles has been widely reported in the literature, posing a frontier challenge in this field. Herein, this topic is revisited and it is demonstrated that X-ray absorption spectra on single-crystalline particles with highly anisotropic lattice structures are sensitive to the polarization configuration of the incident X-rays, causing some degree of ambiguity in analyzing the local spectroscopic fingerprint. To tackle this issue, a methodology is developed that extracts the white-line peak energy in the X-ray absorption near-edge structure spectra as a key data attribute for representing the local state of charge in the LCO crystal. This method demonstrates significantly improved accuracy and reveals the mesoscale chemical complexity in LCO particles with better fidelity. In addition to the implications on the importance of particle engineering for LCO cathodes, the method developed herein also has significant impact on spectro-microscopic studies of single-crystalline materials at synchrotron facilities, which is broadly applicable to a wide range of scientific disciplines well beyond battery research.

Raman micro-spectroscopy monitoring of cytochrome c redox state in Candida utilis during cell death under low-temperature plasma-induced oxidative stress.

Oxidative stress may result in different modes of cell death, such as necrosis, apoptosis and necroptosis. Currently, researchers are still striving to develop efficient tools/methods to distinguish the cell death modes in direct and label-free ways. In this study, we attempted to employ Raman micro-spectroscopy to observe the molecular changes in Candida utilis cells under oxidative stress induced by low-temperature plasma (LTP) and explore the spectroscopic biomarkers for the modes of cell death under oxidative stress. In this research, we confirmed that LTP could impose oxidative stress on the yeast cells, and recorded the changes of Raman signals of cytochrome c in the cells under LTP oxidative stress. Subsequently, we identified the biochemical and morphological characteristic features corresponding to different modes of cell death. Interestingly, we found that LTP under certain conditions could induce oxidative stress which caused the yeast cell death mainly by means of necroptosis, which was verified by Annexin V/PI, HMGB1 location assay and immunoprecipitation assay of the RIP1/RIP3 necrosome. Correspondingly, we also showed that the LTP induced necroptosis, associated with the increase of cytoplasmic Ca2+ and mitochondrial ROS, the decrease of mitochondrial membrane potential, the release of oxidized cytochrome c from the mitochondrion to the cytoplasm, and the destruction of mitochondria in yeast cells. This work has therefore demonstrated that monitoring the redox state of cytochrome c using Raman micro-spectroscopy is very useful for distinguishing the modes of cell death and particularly may unveil the unique necroptosis process of cells under extrinsic oxidative stress.

Optical Detection Method for High Aspect Ratio Microstructures.

High aspect ratio microstructures (HARMS) are of great importance for many application fields. Many defects are generated during the fabrication processes, especially in line microstructures, and it is necessary to examine the quality of the structures after each process. However, there is no suitable efficient nondestructive detection method to monitor microstructures during the fabrication processes. In this paper, an optical detection method capable of detecting the structures by analyzing the reflection of light on the line HARMS is proposed. According to the image of reflected visible light, this method can determine whether there are defects in structures, so as to realize efficient detection. Preliminary simulations and experiments have been performed to confirm the feasibility and validity of the proposed method for detecting line microstructures. This method is expected to obtain more information about microstructures by further optimizing system parameters.

Precise correlative method of Cryo-SXT and Cryo-FM for organelle identification.

Cryogenic soft X-ray tomography (Cryo-SXT) is ideally suitable to image the 3D sub-cellular architecture and organization of cells with high resolution in the near-native preservation state. Cryogenic fluorescence microscopy (Cryo-FM) can determine the location of a molecule of interest that has been labeled with a fluorescent tag, thus revealing the function of the cells. To understand the relations between the sub-cellular architecture and the function of cells, correlative Cryo-SXT and Cryo-FM was applied. This method required the matching of images of different modalities, and the accuracy of the matching is important. Here, a precise correlative method of Cryo-SXT and Cryo-FM is introduced. The capability of matching images of different modalities with high resolution was verified by simulations and practical experiments, and the method was used to identify vacuoles and mitochondria.

From Cubes to Dice: Solvent-Regulated Morphology Engineering of Endohedral Fullerene Microcrystals with Anomalous Photoluminescence Enhancement.

Despite recent successes in preparing three-dimensional crystals of empty fullerenes, such as C60 and C70 , 3D endohedral fullerene crystals, and especially hollow nanostructures, have been scarcely reported. A universal approach has now been developed to prepare shape-tunable 3D crystals of several metal nitride clusterfullerenes, including cubes and dice (hollow cubes with holes at the center of each face), which can be readily switched by changing the volume ratio of good (mesitylene) and poor (isopropanol) solvents. Synchrotron-based soft X-ray nano-computed tomography was used to unambiguously identify the interior microstructure of the dice-shaped crystals of Tb3 N@C80 , and especially the depth of the hole at each face, confirming that the dice has a solid center and the holes are not interconnected. Owing to the enhanced light absorption, the dice-shaped crystals exhibit enhanced photoluminescence relative to that of the cubes.

A modified discrete tomography for improving the reconstruction of unknown multi-gray-level material in the `missing wedge' situation.

Full angular rotational projections cannot always be acquired in tomographic reconstructions because of the limited space in the experimental setup, leading to the `missing wedge' situation. In this paper, a recovering `missing wedge' discrete algebraic reconstruction technique algorithm (rmwDART) has been proposed to solve the `missing wedge' problem and improve the quality of the three-dimensional reconstruction without prior knowledge of the material component's number or the material's values. By using oversegmentation, boundary extraction and mathematical morphological operations, `missing wedge' artifact areas can be located. Then, in the iteration process, by updating the located areas and regions, high-quality reconstructions can be obtained from the simulations, and the reconstructed images based on the rmwDART algorithm can be obtained from soft X-ray nano-computed tomography experiments. The results showed that there is the potential for discrete tomography.

Utilization of Resist Stencil Lithography for Multidimensional Fabrication on a Curved Surface.

The limited ability to fabricate nanostructures on nonplanar rugged surfaces has severely hampered the applicability of many emerging technologies. Here we report a resist stencil lithography based approach for in situ fabrication of multidimensional nanostructures on both planar and uneven substrates. By using the resist film as a flexible stencil to form a suspending membrane with predesigned patterns, a variety of nanostructures have been fabricated on curved or uneven substrates of diverse morphologies on demand. The ability to realize 4 in. wafer scale fabrication of nanostructures as well as line width resolution of sub-20 nm is also demonstrated. Its extraordinary capacity is highlighted by the fabrication of three-dimensional wavy nanostructures with diversified cell morphologies on substrates of different curvatures. A robust general scheme is also developed to construct various complex 3D nanostructures. The use of conventional resists and processing ensures the versatility of the method. Such an in situ lithography technique has offered exciting possibilities to construct nanostructures with high dimensionalities that can otherwise not be achieved with existing nanofabrication methods.