High-efficiency focusing and imaging by dielectric kinoform zone plate lenses with soft X-rays.

With fast advances in enhancing the focusing/imaging resolution of Fresnel zone plate lenses toward sub-10 nm, low diffraction efficiency in connection with their rectangular zone shape still remains a big issue in both soft and hard X-ray microscopy. In hard X-ray optics, encouraging progress has recently been reported in our earlier attempts of high focusing efficiency by 3D kinoform shaped metallic zone plates, formed by greyscale electron beam lithography. This paper addresses our efforts towards high focusing/imaging efficiency by developing a novel dielectric kinoform zone plate lens for soft X-rays. The effects of the zone materials and zone shapes on the focusing/imaging quality were first theoretically investigated by a modified thin-grating-approximation method, revealing superior efficiencies of dielectric kinoform zone plates over rectangular ones in metals. Optical characterizations of replicated dielectric kinoform zone plates by greyscale electron beam lithography demonstrate a focusing efficiency of 15.5% with a resolution of 110 nm in the water window of X-rays. Apart from high efficiency, the novel kinoform zone plate lenses developed in this work exhibit significant advantages over conventional zone plates, i.e. simplified process, low cost and no need for a beamstop.

A compound Kinoform/Fresnel zone plate lens with 15 nm resolution and high efficiency in soft x-ray.

X-ray microscope as an important nanoprobing tool plays a prevailing role in nano-inspections of materials. Despite the fast advances of high resolution focusing/imaging reported, the efficiency of existing high-resolution zone plates is mostly around 5% in soft x-ray and rapidly goes down to 1%-2% when the resolution approaches 10 nm. It is well known that the rectangular zone shape, beamstop, limited height/width ratios, material absorption of light and structural defects are likely responsible for the limited efficiency. Although zone plates with Kinoform profile are supposed to be efficient, progress for achieving both high resolution (<30 nm) and high efficiency (>5%) have hardly been addressed in soft x-ray. In this work, we propose a compound Kinoform/Fresnel zone plate (CKZP) by combing a dielectric Kinoform zone plate with a 15 nm resolution zone plate. Greyscale electron beam lithography was applied to form the 3D Kinoform zone plate and atomic layer deposition was carried out to form the binary zone plate. Optical characterizations demonstrated 15 nm resolution focusing/imaging with over 7.8% efficiency in soft x-ray. The origin of the efficiency improvement behind the proposed compound lens is theoretically analyzed and discussed.

Trapezoid-kinoform zone plate lens - a solution for efficient focusing in hard X-ray optics.

X-ray microscopes are powerful tools in the nano-inspection of materials owing to their ultra-high resolution at the molecular level. However, the focusing efficiency of binary zone plate lenses as key components in such probes is merely 5% in practice, hindering their application in advanced scientific research. Although kinoform zone plate lenses are in principle supposed to possess high efficiency beyond binary ones, little progress has been reported so far due to the shortage of both a theoretical calculation approach and greyscale lithography for generating fine three-dimensional (3D) kinoform zones of the lenses. This paper reports our theoretical work for a modified beam propagation method to compute the focusing performance and state-of-the-art 3D greyscale electron beam lithography for kinoform zone plate lenses. Three different zone shapes - binary, kinoform and top-flat kinoform (nicknamed the trapezoid-kinoform) - were compared both theoretically and experimentally. Theoretical calculations suggest, for the first time, that the trapezoid-kinoform zone plate gives rise to the highest focusing efficiency among the three lenses, which was proved by optical characterization of the fabricated lens with hard X-rays. As high as 40% of the focusing efficiency by Au trapezoid-kinoform lenses with resolution of 250 nm at 8 keV has been achieved, which is two times higher than that of binary zone plate lenses. The origin of the enhanced efficiency in the trapezoid-kinoform zone plate lens was explained by the joint contributions from both the refraction through the kinoform slope and the diffraction through the top flat part of the trapezoid-kinoform zone plate. Such a breakthrough in focusing efficiency sheds light on the further development of X-ray lenses with both high resolution and high efficiency.

Evidence of cell surface iron speciation of acidophilic iron-oxidizing microorganisms in indirect bioleaching process.

While indirect model has been widely accepted in bioleaching, but the evidence of cell surface iron speciation has not been reported. In the present work the iron speciation on the cell surfaces of four typically acidophilic iron-oxidizing microorganism (mesophilic Acidithiobacillus ferrooxidans ATCC 23270, moderately thermophilic Leptospirillum ferriphilum YSK and Sulfobacillus thermosulfidooxidans St, and extremely thermophilic Acidianus manzaensis YN25) grown on different energy substrates (chalcopyrite, pyrite, ferrous sulfate and elemental sulfur (S(0))) were studied in situ firstly by using synchrotron-based micro- X-ray fluorescence analysis and X-ray absorption near-edge structure spectroscopy. Results showed that the cells grown on iron-containing substrates had apparently higher surface iron content than the cells grown on S(0). Both ferrous iron and ferric iron were detected on the cell surface of all tested AIOMs, and the Fe(II)/Fe(III) ratios of the same microorganism were affected by different energy substrates. The iron distribution and bonding state of single cell of A. manzaensis were then studied in situ by scanning transmission soft X-ray microscopy based on dual-energy contrast analysis and stack analysis. Results showed that the iron species distributed evenly on the cell surface and bonded with amino, carboxyl and hydroxyl groups.

Differential expression of extracellular thiol groups of moderately thermophilic Sulfobacillus thermosulfidooxidans and extremely thermophilic Acidianus manzaensis grown on S(0) and Fe (2.).

Bio-oxidation of elemental sulfur (S(0)) is very important in bioleaching and sulfur cycle. S(0) was proposed to be first activated by reacting with reactive thiol groups (-SH) of outer membrane proteins, forming -S n H (n ≥ 2) complexes. The differential expression of -SH of moderately thermophilic Sulfobacillus thermosulfidooxidans and extremely thermophilic Acidianus manzaensis grown on Fe(2+) and S(0) was investigated by synchrotron radiation-based scanning transmission X-ray microscopy (STXM) imaging and micro-beam X-ray fluorescence (µ-XRF) mapping. The STXM imaging and µ-XRF mapping of extracellular -SH were based on the analysis of Ca(2+) bound on the cell. By comparing Ca(2+) of the cells with and without labeling by Ca(2+), the distribution and content of thiol groups were obtained. The results showed that, for both S. thermosulfidooxidans and A. manzaensis, the expression of extracellular -SH of S(0)-grown cells was higher than that of Fe(2+)-grown cells. Statistical analysis indicated that the expression of extracellular -SH for S. thermosulfidooxidans and A. manzaensis grown on S(0) was 2.37 times and 2.14 times, respectively, to that on Fe(2+). These results evidently demonstrate that the extracellular thiol groups are most probably involved in elemental sulfur activation and oxidation of the acidophilic sulfur-oxidizing microorganisms.

A COOH-terminated nitrogen-doped carbon aerogel as a bulk electrode for completely selective two-electron oxygen reduction to H2O2.

A COOH-terminated nitrogen-doped carbon aerogel exhibited 100% selectivity to two-electron oxygen reduction, exceeding reported carbonaceous and noble metal catalysts. The optimal electrode with the synergistic effect of C-N/C-COOH resulted in a minimum ηO2/H2O2 and gave an evolution rate of 60 mg L-1 g-1 h-1 for H2O2 with satisfactory mechanical and electrochemical stability for practical applications.

Soft x-ray spectroscopic endstation at beamline 08U1A of Shanghai Synchrotron Radiation Facility.

A spectroscopic endstation with magnetic field, voltage, and low temperature control has been installed and commissioned at the soft X-ray beamline 08U1A of Shanghai Synchrotron Radiation Facility, which can obtain a magnetic field up to ±0.53 T, applied current and bias voltage, and cryogenic temperatures down to 14 K with a Gifford-McMahon cycle cryocooler. The endstation can perform soft X-ray absorption spectroscopy methods including total electron yield, fluorescence yield, and X-ray excited optical luminance. Combined with an elliptically polarized undulator and the in situ conditions, the endstation can effectively perform X-ray magnetic circular and linear dichroism experiments in the soft X-ray range between photon energies of 250 and 2000 eV.

In situ characterization of change in superficial organic components of thermoacidophilic archaeon Acidianus manzaensis YN-25.

For the first time, synchrotron radiation (SR) -based carbon K-edge X-ray absorption near edge structure (XANES) spectroscopy in-situ characterization was conducted to evaluate the evolution of superficial (about 10 nm) organic components of extracellular polymeric substances (EPS) of thermoacidophilic archaeon Acidianus manzaensis YN-25 acclimated with different energy substrates (FeS2, CuFeS2, S0, FeSO4). The atomic force microscopy (AFM) morphology scanning showed that the strain acclimated with different energy substrates varied a lot in EPS amount. XANES results showed clear associations between the energy substrates and the changes in organic composition in terms of typical function groups (CO, CO and CN). The chalcopyrite- and pyrite-acclimated cells contained higher proportion of proteins but less proportion of polysaccharides than the S0-acclimated cells. The FeSO4-acclimated cells contained the highest proportion of proteins, while the S0-acclimated cells contained more lipids and polysaccharides. The results of linear-combination and peak fitting of the K-edge XANES for the extracellular superficial organic component C is consistent with the trend in comparison with the results of FTIR and spectrophotometric determination, but there are significant differences in the values. These differences are caused by the inconsistencies of measurement depth between XANES and the latter two characterization methods.

Chromium immobilization by extra- and intraradical fungal structures of arbuscular mycorrhizal symbioses.

Arbuscular mycorrhizal (AM) fungi can enhance plant Cr tolerance through immobilizing Cr in mycorrhizal roots. However, the detailed processes and mechanisms are unclear. The present study focused on cellular distribution and speciation of Cr in both extraradical mycelium (ERM) and mycorrhizal roots exposed to Cr(VI) by using field emission scanning electron microscopy equipped with energy dispersive X-ray spectrometer (FE-SEM-EDS), scanning transmission soft X-ray microscopy (STXM) and X-ray absorption fine structure (XAFS) spectroscopy techniques. We found that amounts of particles (possibly extracellular polymeric substances, EPS) were produced on the AM fungal surface upon Cr(VI) stress, which contributed greatly to Cr(VI) reduction and immobilization. With EDS of the surface of AM fungi exposed to various Cr(VI) levels, a positive correlation between Cr and P was revealed, suggesting that phosphate groups might act as counter ions of Cr(III), which was also confirmed by the XAFS analysis. Besides, STXM and XAFS analyses showed that Cr(VI) was reduced to Cr(III) in AM fungal structures (arbuscules, intraradical mycelium, etc.) and cell walls in mycorrhizal roots, and complexed possibly with carboxyl groups or histidine analogues. The present work provided evidence of Cr immobilization on fungal surface and in fungal structures in mycorrhizal roots at a cellular level, and thus unraveled the underlying mechanisms by which AM symbiosis immobilize Cr.

Translocation and biotransformation of CuO nanoparticles in rice (Oryza sativa L.) plants.

Metal-based nanoparticles (MNPs) may be translocated and biochemically modified in vivo, which may influence the fate of MNPs in the environment. Here, synchrotron-based techniques were used to investigate the behavior of CuO NPs in rice plants exposed to 100 mg/L CuO NPs for 14 days. Micro X-ray fluorescence (µ-XRF) and micro X-ray absorption near edge structure (µ-XANES) analysis revealed that CuO NPs moved into the root epidermis, exodermis, and cortex, and they ultimately reached the endodermis but could not easily pass the Casparian strip; however, the formation of lateral roots provided a potential pathway for MNPs to enter the stele. Moreover, bulk-XANES data showed that CuO NPs were transported from the roots to the leaves, and that Cu (II) combined with cysteine, citrate, and phosphate ligands and was even reduced to Cu (I). CuO NPs and Cu-citrate were observed in the root cells using soft X-ray scanning transmission microscopy (STXM).

Synchrotron radiation based STXM analysis and micro-XRF mapping of differential expression of extracellular thiol groups by Acidithiobacillus ferrooxidans grown on Fe(2+) and S(0).

The differential expression of extracellular thiol groups by Acidithiobacillus ferrooxidans grown on substrates Fe(2+) and S(0) was investigated by using synchrotron radiation based scanning transmission X-ray microscopy (STXM) imaging and microbeam X-ray fluorescence (µ-XRF) mapping. The extracellular thiol groups (SH) were first alkylated by iodoacetic acid forming Protein-SCH2COOH and then the P-SCH2COOH was marked by calcium ions forming P-SCH2COOCa. The STXM imaging and µ-XRF mapping of SH were based on analysis of SCH2COO-bonded Ca(2+). The results indicated that the thiol group content of A. ferrooxidans grown on S(0) is 3.88 times to that on Fe(2+). Combined with selective labeling of SH by Ca(2+), the STXM imaging and µ-XRF mapping provided an in situ and rapid analysis of differential expression of extracellular thiol groups.

High-performance soft x-ray spectromicroscopy beamline at SSRF.

The Shanghai Synchrotron Radiation Facility (SSRF) is the first third-generation synchrotron facility in China and operated at an electron energy of 3.5 GeV. One of the seven beamlines in the first construction phase is devoted to soft x-ray spectromicroscopy and is equipped with an elliptically polarized undulator light source, a plane grating monochromator, and a scanning transmission x-ray microscope end station. Initial results reveal the high performance of this beamline, with an energy resolving power estimated to be over 10,000 at the argon L-edge and a spatial resolution better than 30 nm.