Multidecadally resolved polarity oscillations during a geomagnetic excursion.

Polarity reversals of the geomagnetic field have occurred through billions of years of Earth history and were first revealed in the early 20th century. Almost a century later, details of transitional field behavior during geomagnetic reversals and excursions remain poorly known. Here, we present a multidecadally resolved geomagnetic excursion record from a radioisotopically dated Chinese stalagmite at 107-91 thousand years before present with age precision of several decades. The duration of geomagnetic directional oscillations ranged from several centuries at 106-103 thousand years before present to millennia at 98-92 thousand years before present, with one abrupt reversal transition occurring in one to two centuries when the field was weakest. These features indicate prolonged geodynamo instability. Repeated asymmetrical interhemispheric polarity drifts associated with weak dipole fields likely originated in Earth's deep interior. If such rapid polarity changes occurred in future, they could severely affect satellites and human society.

The Origin of Capacity Fade in the Li2MnO3·LiMO2 (M = Li, Ni, Co, Mn) Microsphere Positive Electrode: An Operando Neutron Diffraction and Transmission X-ray Microscopy Study.

The mechanism of capacity fade of the Li2MnO3·LiMO2 (M = Li, Ni, Co, Mn) composite positive electrode within a full cell was investigated using a combination of operando neutron powder diffraction and transmission X-ray microscopy methods, enabling the phase, crystallographic, and morphological evolution of the material during electrochemical cycling to be understood. The electrode was shown to initially consist of 73(1) wt % R3̅m LiMO2 with the remaining 27(1) wt % C2/m Li2MnO3 likely existing as an intergrowth. Cracking in the Li2MnO3·LiMO2 electrode particle under operando microscopy observation was revealed to be initiated by the solid-solution reaction of the LiMO2 phase on charge to 4.55 V vs Li(+)/Li and intensified during further charge to 4.7 V vs Li(+)/Li during the concurrent two-phase reaction of the LiMO2 phase, involving the largest lattice change of any phase, and oxygen evolution from the Li2MnO3 phase. Notably, significant healing of the generated cracks in the Li2MnO3·LiMO2 electrode particle occurred during subsequent lithiation on discharge, with this rehealing being principally associated with the solid-solution reaction of the LiMO2 phase. This work reveals that while it is the reduction of lattice size of electrode phases during charge that results in cracking of the Li2MnO3·LiMO2 electrode particle, with the extent of cracking correlated to the magnitude of the size change, crack healing is possible in the reverse solid-solution reaction occurring during discharge. Importantly, it is the phase separation during the two-phase reaction of the LiMO2 phase that prevents the complete healing of the electrode particle, leading to pulverization over extended cycling. This work points to the minimization of behavior leading to phase separation, such as two-phase and oxygen evolution, as a key strategy in preventing capacity fade of the electrode.

Synthesis of novel chitosan/sodium hyaluronate/iridium hydrogel nanocomposite for wound healing application.

A novel chitosan/sodium hyaluronate/iridium (CHI/SH/Ir) hydrogel nanocomposite with a unique microstructure containing vertically aligned pores is fabricated via an electrophoresis technique. The formation of orderly vertical pores in CHI/SH/Ir hydrogel nanocomposite is due to the confinement of hydrogen bubbles produced from the water electrolysis during electrophoresis that limits their lateral movement and coalescence. In a wet state, the diameter for the vertical pores is 600-700 µm. With a thickness of 500 µm, the CHI/SH/Ir hydrogel nanocomposite exhibits a porosity of 76.7 % and a water uptake of 350 %. Its tensile strength is almost doubled to 8.7 MPa, as compared to that of counterpart without the addition of iridium. In CHI/SH/Ir hydrogel nanocomposite, the iridium nanoparticles are homogeneously distributed with an average size of 3 nm. The CHI/SH/Ir electrophoresis suspension exhibits a negligible cytotoxicity. In cell migration test using the human keratinocytes HaCaT cells, the CHI/SH/Ir hydrogel nanocomposite reveals a relative migration of 122.15 ± 9.02 % (p < 0.001) as compared to the blank sample. The presence of vertically aligned pores with the use of SH and iridium nanoparticles indicates a promising opportunity in wound healing application.

Site-specific thrombus formation: advancements in photothrombosis-on-a-chip technology.

Thrombosis, characterized by blood clot formation within vessels, poses a significant medical challenge. Despite extensive research, the development of effective thrombosis therapies is hindered by substantial costs, lengthy development times, and high failure rates in medication commercialization. Conventional pre-clinical models often oversimplify cardiovascular disease, leading to a disparity between experimental results and human physiological responses. In response, we have engineered a photothrombosis-on-a-chip system. This microfluidic model integrates human endothelium, human whole blood, and blood flow dynamics and employs the photothrombotic method. It enables precise, site-specific thrombus induction through controlled laser irradiation, effectively mimicking both normal and thrombotic physiological conditions on a single chip. Additionally, the system allows for the fine-tuning of thrombus occlusion levels via laser parameter adjustments, offering a flexible thrombus model with varying degrees of obstruction. Additionally, the formation and progression of thrombosis noted on the chip closely resemble the thrombotic conditions observed in mice in previous studies. In the experiments, we perfused recalcified whole blood with Rose Bengal into an endothelialized microchannel and initiated photothrombosis using green laser irradiation. Various imaging methods verified the model's ability to precisely control thrombus formation and occlusion levels. The effectiveness of clinical drugs, including heparin and rt-PA, was assessed, confirming the chip's potential in drug screening applications. In summary, the photothrombosis-on-a-chip system significantly advances human thrombosis modeling. Its precise control over thrombus formation, flexibility in the thrombus severity levels, and capability to simulate dual physiological states on a single platform make it an invaluable tool for targeted drug testing, furthering the development of organ-on-a-chip drug screening techniques.

Formation of diverse supercrystals from self-assembly of a variety of polyhedral gold nanocrystals.

Cubic, rhombic dodecahedral, octahedral, and corner-truncated octahedral gold nanocrystals with sizes of tens of nanometers have been used as building blocks to form micrometer-sized supercrystals by slowly evaporating a water droplet on a substrate placed in a moist environment. Drying the droplet at 90 °C was found to yield the best supercrystals. Supercrystals were evenly distributed throughout the entire substrate surface originally covered by the droplet. Diverse supercrystal morphologies have been observed. Nanocubes formed roughly cubic supercrystals. Rhombic dodecahedra were assembled into truncated triangular pyramidal supercrystals. Rhombic dodecahedral, octahedral, and hexapod-shaped supercrystals were generated through the assembly of octahedra. Corner-truncated octahedra formed tetrapod-shaped supercrystals at room temperature, but octahedral, truncated triangular pyramidal, and square pyramidal supercrystals at 90 °C. Nanocrystal assembly was found to be strongly shape-guided. Expulsion of excess surfactant to the surfaces of supercrystals suggests that responsive adjustment of surfactant concentration during particle assembly mediates supercrystal formation. Transmission X-ray microscopy and optical microscopy have been employed to follow the supercrystal formation process. Surprising rotational water current near the droplet perimeter carrying the initially formed supercrystals has been observed. Supercrystals appear to grow from the edge of the droplet toward the central region. Supercrystals assembled from octahedra inherently contain void spaces and possibly connected channels. The mesoporosity of these supercrystals was confirmed by infiltrating H(2)PdCl(4) into the supercrystal interior and reducing the precursor to form Pd nanoparticles. The embedded Pd particles can still catalyze a Suzuki coupling reaction, demonstrating the application of these supercrystals for molecular transport, sensing, and catalysis.

Assessment of metabolic modulation in free-living versus endosymbiotic Symbiodinium using synchrotron radiation-based infrared microspectroscopy.

The endosymbiotic relationship between coral hosts and dinoflagellates of the genus Symbiodinium is critical for the growth and productivity of coral reef ecosystems. Here, synchrotron radiation-based infrared microspectroscopy was applied to examine metabolite concentration differences between endosymbiotic (within the anemone Aiptasia pulchella) and free-living Symbiodinium over the light-dark cycle. Significant differences in levels of lipids, nitrogenous compounds, polysaccharides and putative cell wall components were documented. Compared with free-living Symbiodinium, total lipids, unsaturated lipids and polysaccharides were relatively enriched in endosymbiotic Symbiodinium during both light and dark photoperiods. Concentrations of cell wall-related metabolites did not vary temporally in endosymbiotic samples; in contrast, the concentrations of these metabolites increased dramatically during the dark photoperiod in free-living samples, possibly reflecting rhythmic cell-wall synthesis related to light-driven cell proliferation. The level of nitrogenous compounds in endosymbiotic cells did not vary greatly across the light-dark cycle and in general was significantly lower than that observed in free-living samples collected during the light. Collectively, these data suggest that nitrogen limitation is a factor that the host cell exploits to induce the biosynthesis of lipids and polysaccharides in endosymbiotic Symbiodinium.

Slip zone and energetics of a large earthquake from the Taiwan Chelungpu-fault Drilling Project.

Determining the seismic fracture energy during an earthquake and understanding the associated creation and development of a fault zone requires a combination of both seismological and geological field data. The actual thickness of the zone that slips during the rupture of a large earthquake is not known and is a key seismological parameter in understanding energy dissipation, rupture processes and seismic efficiency. The 1999 magnitude-7.7 earthquake in Chi-Chi, Taiwan, produced large slip (8 to 10 metres) at or near the surface, which is accessible to borehole drilling and provides a rare opportunity to sample a fault that had large slip in a recent earthquake. Here we present the retrieved cores from the Taiwan Chelungpu-fault Drilling Project and identify the main slip zone associated with the Chi-Chi earthquake. The surface fracture energy estimated from grain sizes in the gouge zone of the fault sample was directly compared to the seismic fracture energy determined from near-field seismic data. From the comparison, the contribution of gouge surface energy to the earthquake breakdown work is quantified to be 6 per cent.

Advantages and limitations of the synchrotron based transmission X-ray microscopy in the study of the clay aggregate structure in aqueous suspensions.

This paper reports new application of new transmission X-ray microscopy powered by a synchrotron source for the study of aqueous based clay suspensions. This paper delineates the advantages and limitations of this method. The tested transmission X-ray microscopy (TXM) technique has shown good agreement with the cryo-stage SEM technique. The spacial resolution of this TXM technique is 60 nm and clay particles with diameter below 500 nm are clearly visible and their pseudohexagonal symmetry is recognizable in detail. It is clearly demonstrated the methodology of implementing TXM to study aqueous based clay suspensions that are close to approximately 60 nm tomographic resolution. The technique enables us to study discrete structure of clay suspensions in water and within aggregates. This has never been previously possible. Larger crystals, more compact aggregates and less colloidal fraction present in kaolinite from Georgia has impact on faster settling and gelling in denser suspension than for Birdwood kaolinite in which colloidal particles create gel-like networking in less dense aqueous suspension.

Transmission X-ray microscopy reveals the clay aggregate discrete structure in aqueous environment.

The utilization of new transmission X-ray microscopy (TXM) using the synchrotron photon source enable for the first time the study in three dimensions microsize clay particles in aggregates in their natural aqueous environment. This technique makes possible remarkable accurate images of nanosize mineral interparticle structure which forms a new nanocomposite. The Birdwood kaolinite/LDH aggregates observed in the TXM are much more compact than observed before in pure Birdwood kaolinite suspension and similar to aggregates formed after treatment by positively charged surfactant. Kaolinite/LDH aggregates in water reveal complex structure of larger kaolinite platelets connected together by gelled nanoparticles which are most probably LDH colloidal plates. Comparisons of the transmission electron microscope (TEM) and TXM techniques show similarities in particle morphology. The ability to study particles and aggregates in their natural aqueous environment and in 3-dimensions make this technique superior to the TEM technique.

Evolution and Function of Dinosaur Teeth at Ultramicrostructural Level Revealed Using Synchrotron Transmission X-ray Microscopy.

The relationship between tooth form and dietary preference is a crucial issue in vertebrate evolution. However, the mechanical properties of a tooth are influenced not only by its shape but also by its internal structure. Here, we use synchrotron transmission X-ray microscopy to examine the internal microstructures of multiple dinosaur teeth within a phylogenetic framework. We found that the internal microstructures of saurischian teeth are very different from advanced ornithischian teeth, reflecting differences in dental developmental strategies. The three-tissue composition (enamel-mantle dentin-bulk dentin) near the dentinoenamel junction (DEJ) in saurischian teeth represents the primitive condition of dinosaur teeth. Mantle dentin, greatly reduced or absent from DEJ in derived ornithischian teeth, is a key difference between Saurischia and Ornithischia. This may be related to the derived herbivorous feeding behavior of ornithischians, but interestingly, it is still retained in the herbivorous saurischian sauropods. The protective functions of mantle dentin with porous microstructures between enamel and bulk dentin inside typical saurischian teeth are also discussed using finite-element analysis method. Evolution of the dental modifications in ornithischian dinosaurs, with the absence of mantle dentin, may be related to changes in enamel characteristics with enamel spindles extending through the DEJ.

The formation of a structural framework in gelled Wyoming bentonite: direct observation in aqueous solutions.

HYPOTHESIS: Particle space arrangement is a very important factor that determines the physico-mechanical properties of soil. Formations of three-dimensional (3D) structured networks within gelled or flocculated suspension may prevent clay particles and aggregates from settling under gravity force and by encapsulate water within such a network, lead to poor sludge dewatering. To better understand this phenomenon, a microstructural investigation of a smectite clay (SWy2) suspension was conducted. EXPERIMENTS: SWy-2 was diluted in water and a moderately salty aqueous solution and was studied with the aid of a synchrotron-powered transmission X-ray microscope (TXM) and cryogenic transmission electron microscope (Cryo-TEM). Observations of mutual particle arrangement in 3D spaces were conducted within a natural water environment after vitrification without drying. FINDINGS: A new type of micro-architecture in particle space arrangement was observed. Smectite flakes were mostly in edge-to-edge (EE) contact and formed a 3D network, confirming a "net of flakes" structural model. Clay particles form a complex and multi-hierarchic flocculated structure with characteristic cellular chained networking. Chained aggregates build cellular elements, encapsulating water inside closed voids. Increasing ionic strength results in the development of multi-hierarchic voids categories, with most water retained within nano-pores.

Structural characterization of colloidal crystals and inverse opals using transmission X-ray microscopy.

A nondestructive tomographic technique was used to determine the crystallographic information of colloidal crystals comprising of polystyrene (PS) microspheres, as well as their silver inverse opals. The properties of the colloidal crystals, such as defects, grain size, grain boundaries, stacking sequence, and grain orientation, were determined using the full field transmission X-ray microscopy (TXM) with a spatial resolution of 50 nm. The PS microspheres (500-750 nm) which underwent a vertical electrophoresis process to form a face-centered cubic (fcc) close-packed structure with an ABCABC packing sequence. In addition, the colloidal crystal exhibited multiple grains, and an orientation variation of 6.1° in the stacking direction between two neighboring grains.

Kaolinite flocculation induced by smectite addition - a transmission X-ray microscopic study.

The influence of smectite addition on kaolinite suspensions in water was investigated by transmission X-ray microscopy (TXM) and Scanning Electron Microscopy (SEM). Sedimentation test screening was also conducted. Micrographs were processed by the STatistic IMage Analysing (STIMAN) program and structural parameters were calculated. From the results of the sedimentation tests important influences of small smectite additions to about 3wt.% on kaolinite suspension flocculation has been found. In order to determine the reason for this smectite impact on kaolinite suspension, macroscopic behaviour micro-structural examination using Transmission X-ray Microscope (TXM) and SEM has been undertaken. TXM & SEM micrographs of freeze-dried kaolinite-smectite suspensions with up to 20% smectite showed a high degree of orientation of the fabric made of highly oriented particles and greatest density when 3wt.% of smectite was added to the 10wt.% dense kaolinite suspension. In contrast, suspensions containing pure kaolinite do not show such platelet mutual orientation but homogenous network of randomly oriented kaolinite platelets. This suggests that in kaolinite-smectite suspensions, smectite forms highly oriented basic framework into which kaolinite platelets may bond in face to face preferential contacts strengthening structure and allowing them to show plastic behaviour which is cause of platelets orientation.

Smectite flocculation structure modified by Al13 macro-molecules--as revealed by the transmission X-ray microscopy (TXM).

The aggregate structure which occurs in aqueous smectitic suspensions is responsible for poor water clarification, difficulties in sludge dewatering and the unusual rheological behaviour of smectite rich soils. These macroscopic properties are dictated by the 3D structural arrangement of smectite finest fraction within flocculated aggregates. Here, we report results from a relatively new technique, transmission X-ray microscopy (TXM), which makes it possible to investigate the internal structure and 3D tomographic reconstruction of the smectite clay aggregates modified by Al(13) Keggin macro-molecule [Al(13)(O)(4)(OH)(24)(H(2)O)(12)](7+). Three different treatment methods were shown resulted in three different micro-structural environments of the resulting flocculation. In case of smectite sample prepared in Methods 1 and 3 particles fall into the primary minimum where Van der Waals forces act between FF oriented smectite flakes and aggregates become approach irreversible flocculation. In case of sample prepared using Method 2, particles contacting by edges (EE) and edge to face (EF) orientation fell into secondary minimum and weak flocculation resulted in severe gelation and formation of the micelle-like texture in fringe superstructure, which was first time observed in smectite based gel.

A dedicated small-angle X-ray scattering beamline with a superconducting wiggler source at the NSRRC.

At the National Synchrotron Radiation Research Center (NSRRC), which operates a 1.5 GeV storage ring, a dedicated small-angle X-ray scattering (SAXS) beamline has been installed with an in-achromat superconducting wiggler insertion device of peak magnetic field 3.1 T. The vertical beam divergence from the X-ray source is reduced significantly by a collimating mirror. Subsequently the beam is selectively monochromated by a double Si(111) crystal monochromator with high energy resolution (DeltaE/E approximately 2 x 10(-4)) in the energy range 5-23 keV, or by a double Mo/B4C multilayer monochromator for 10-30 times higher flux ( approximately 10(11) photons s(-1)) in the 6-15 keV range. These two monochromators are incorporated into one rotating cradle for fast exchange. The monochromated beam is focused by a toroidal mirror with 1:1 focusing for a small beam divergence and a beam size of approximately 0.9 mm x 0.3 mm (horizontal x vertical) at the focus point located 26.5 m from the radiation source. A plane mirror installed after the toroidal mirror is selectively used to deflect the beam downwards for grazing-incidence SAXS (GISAXS) from liquid surfaces. Two online beam-position monitors separated by 8 m provide an efficient feedback control for an overall beam-position stability in the 10 microm range. The beam features measured, including the flux density, energy resolution, size and divergence, are consistent with those calculated using the ray-tracing program SHADOW. With the deflectable beam of relatively high energy resolution and high flux, the new beamline meets the requirements for a wide range of SAXS applications, including anomalous SAXS for multiphase nanoparticles (e.g. semiconductor core-shell quantum dots) and GISAXS from liquid surfaces.

Transmission X-ray microscopy (TXM) reveals the nanostructure of a smectite gel.

The unusual behavior of smectites, the ability to change volume when wetted (swelling) or dried (shrinking), makes soil rich in smectites very unstable and dangerous for the building industry because of the movement of building foundations and poor slope stability. These macroscopic properties are dominated by the structural arrangement of the smectites' finest fraction. Here, we show in three dimensions how the swelling phenomenon in smectite, caused by a combination of hydratation and electrostatic forces, may expand the dry smectite volume not 10-fold, as previously thought, but to more than 1000-fold. A new technique, transmission X-ray microscopy, makes it possible to investigate the internal structure and 3-D tomographic reconstruction of clay aggregates. This reveals, for the first time, the smectite gel arrangement in the voluminous cellular tactoid structure within a natural aqueous environment.

Cost-effective upgrade of a focusing system for inelastic X-ray scattering experiments under high pressure.

Inelastic X-ray scattering (IXS) is a powerful technique capable of probing the dynamic behavior and electronic structure of materials. For IXS experiments under high pressure up to the megabar range using state-of-the-art diamond-anvil-cell technology, the sample volume is limited to the order of 1 x 10(-3) mm(3) for which a beam focus of the same order and less is often required. In this paper a scheme utilizing a set of low-cost and compact Kirkpatrick-Baez mirrors for upgrading the existing optical system of the Taiwan IXS beamline at SPring-8 is described. The scheme as implemented improves the focus to 13 microm x 16 microm (horizontal x vertical) with a transmission of up to 72% and a flux density gain of over 30 times, which has enhanced substantially the efficiency of the beamline for high-pressure research.

X-ray beamlines for structural studies at the NSRRC superconducting wavelength shifter.

Using a superconducting-wavelength-shifter X-ray source with a photon flux density of 10(11)-10(13) photons s(-1) mrad(-1) (0.1% bandwidth)(-1) (200 mA)(-1) in the energy range 5-35 keV, three hard X-ray beamlines, BL01A, BL01B and BL01C, have been designed and constructed at the 1.5 GeV storage ring of the National Synchrotron Radiation Research Center (NSRRC). These have been designed for structure-related research using X-ray imaging, absorption, scattering and diffraction. The branch beamline BL01A, which has an unmonochromatized beam, is suitable for phase-contrast X-ray imaging with a spatial resolution of 1 microm and an imaging efficiency of one frame per 10 ms. The main beamline BL01B has 1:1 beam focusing and a medium energy resolution of approximately 10(-3). It has been designed for small-angle X-ray scattering and transmission X-ray microscopy, used, respectively, in anomalous scattering and nanophase-contrast imaging with 30 nm spatial resolution. Finally, the branch beamline BL01C, which features collimating and focusing mirrors and a double-crystal monochromator for a high energy resolution of approximately 10(-4), has been designed for X-ray absorption spectroscopy and high-resolution powder X-ray diffraction. These instruments, providing complementary tools for studying multiphase structures, have opened up a new research trend of integrated structural study at the NSRRC, especially in biology and materials. Examples illustrating the performances of the beamlines and the instruments installed are presented.