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Hsin‐Yi Wang Ying‐Ya Hsu Rong Chen Ting‐Shan Chan Hao Ming Chen Bin Liu 《Liver Transplantation》2015,5(10)
Efficient and earth abundant electrocatalysts for high‐performance oxygen evolution reaction (OER) are essential for the development of sustainable energy conversion technologies. Here, a new hierarchical Ni–Co oxide nanostructure, composed of small secondary nanosheets grown on primary nanosheet arrays, is synthesized via a topotactic transformation of Ni–Co layered double hydroxide. The Ni3+‐rich surface benefits the formation of NiOOH, which is the main redox site as revealed via in situ X‐ray absorption near edge structure and extended X‐ray absorption fine structure spectroscopy. The Ni–Co oxide hierarchical nanosheets (NCO–HNSs) deliver a stable current density of 10 mA cm?2 at an overpotential of ≈0.34 V for OER with a Tafel slope of as low as 51 mV dec?1 in alkaline media. The improvement in the OER activity can be ascribed to the synergy of large surface area offered by the 3D hierarchical nanostructure and the facile formation of NiOOH as the main active sites on the surface of NCO–HNSs to decrease the overpotential and facilitate the catalytic reaction. 相似文献
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Wenchao Huang Eliot Gann Lars Thomsen Cunku Dong Yi‐Bing Cheng Christopher R. McNeill 《Liver Transplantation》2015,5(7)
The microstructure of the polymer PBDTTT‐EFT and blends with the fullerene derivative PC71BM that achieve solar conversion efficiencies of over 9% is comprehensively investigated. A combination of synchrotron techniques are employed including surface‐sensitive near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy and bulk‐sensitive grazing‐incidence wide angle X‐ray scattering (GIWAXS). A preferential “face‐on” orientation of PBDTTT‐EFT is observed in the bulk of both pristine and blend thin films, with π–π stacking largely normal to the substrate, which is thought to be beneficial for charge transport. At the surface of the blend, a slight “edge‐on” structure of the polymer is observed with side‐chains aligned normal to the substrate. The effect of the solvent additive 1,8‐diiodooctane (DIO) on solar cell efficiency and film microstructure is also investigated, where the addition of 3 vol% DIO results in an efficiency increase from ≈6.4% to ≈9.5%. GIWAXS studies indicate that the addition of DIO improves the crystallization of the polymer. Furthermore, atomic force microscopy and transmission electron microscopy are employed to image surface and bulk morphology revealing that DIO suppresses the formation of large PC71BM aggregates. 相似文献
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Operando X‐ray diffraction (XRD) and X‐ray absorption spectroscopy (XAS) studies of Ge anodes are carried out to understand the effect of cycling rate on Ge phase transformation during charge/discharge process and to relate that effect to capacity. It is discovered that the formation of crystalline Li15Ge4 (c‐Li15Ge4) during lithiation is suppressed beyond a certain cycling rate. A very stable and reversible high capacity of ≈1800 mAh g?1 can be attained up to 100 cycles at a slow C‐rate of C/21 when there is complete conversion of Ge anode into c‐Li15Ge4. When the C‐rate is increased to ≈C/10, the lithiation reaction is more heterogeneous and a relatively high capacity of ≈1000 mAh g?1 is achieved with poorer electrochemical reversibility. An increase in C‐rate to C/5 and higher reduces the capacity (≈500 mAh g?1) due to an impeded transformation from amorphous LixGe to c‐Li15Ge4, and yet improves the electrochemical reversibility. A proposed mechanism is presented to explain the C‐rate dependent phase transformations and the relationship of these to capacity fading. The operando XRD and XAS results provide new insights into the relationship between structural changes in Ge and battery capacity, which are important for guiding better design of high‐capacity anodes. 相似文献
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Haraszti T Trantow CM Hedberg-Buenz A Grunze M Anderson MG 《Pigment cell & melanoma research》2011,24(1):187-196
GPNMB is a unique melanosomal protein. Unlike many melanosomal proteins, GPNMB has not been associated with any forms of albinism, and it is unclear whether GPNMB has any direct influence on melanosomes. Here, melanosomes from congenic strains of C57BL/6J mice mutant for Gpnmb are compared to strain-matched controls using standard transmission electron microscopy and synchrotron-based X-ray absorption near-edge structure analysis (XANES). Whereas electron microscopy did not detect any ultrastructural changes in melanosomes lacking functional GPNMB, XANES uncovered multiple spectral phenotypes. These results directly demonstrate that GPNMB influences the chemical composition of melanosomes and more broadly illustrate the potential for using genetic approaches in combination with nano-imaging technologies to study organelle biology. 相似文献
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The search for superior‐energy‐density electrode materials for rechargeable batteries is prompted by the continuously growing demand for new electric vehicles and large energy‐storage grids. The structural properties of electrode materials affect their electrochemical performance because their functionality is correlated to their structure at the atomic scale. Although challenging, a deeper and comprehensive understanding of the basic structural operating units of electrode materials may contribute to the advancement of new energy‐storage technologies and many other technologies. Therefore, we must strategically control both the structure and kinetics of electrode materials to achieve optimal electrochemical performance. In this contribution, advancements in synchrotron radiation techniques, specifically in situ/operando experiments on electrode materials for rechargeable batteries, are presented and discussed. Indeed, the latest synchrotron radiation methods offer deeper insights into pristine and chemically modified electrode materials, opening new opportunities to optimize these materials and exploit new technologies. In particular, the most recent results from in situ/operando synchrotron radiation measurements, which play a critical role in the fundamental understanding of the kinetics processes that occur in rechargeable batteries, are discussed. 相似文献
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Hirofumi Komori Ryosuke Sugiyama Kunishige Kataoka Kentaro Miyazaki Yoshiki Higuchi Takeshi Sakurai 《Acta Crystallographica. Section D, Structural Biology》2014,70(3):772-779
Structural models determined by X‐ray crystallography play a central role in understanding the catalytic mechanism of enzymes. However, X‐ray radiation generates hydrated electrons that can cause significant damage to the active sites of metalloenzymes. In the present study, crystal structures of the multicopper oxidases (MCOs) CueO from Escherichia coli and laccase from a metagenome were determined. Diffraction data were obtained from a single crystal under low to high X‐ray dose conditions. At low levels of X‐ray exposure, unambiguous electron density for an O atom was observed inside the trinuclear copper centre (TNC) in both MCOs. The gradual reduction of copper by hydrated electrons monitored by measurement of the Cu K‐edge X‐ray absorption spectra led to the disappearance of the electron density for the O atom. In addition, the size of the copper triangle was enlarged by a two‐step shift in the location of the type III coppers owing to reduction. Further, binding of O2 to the TNC after its full reduction was observed in the case of the laccase. Based on these novel structural findings, the diverse resting structures of the MCOs and their four‐electron O2‐reduction process are discussed. 相似文献
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Hwajung Choi Hee Jung Kim Atsushi Matsuura Bunzo Mikami Hye‐Jin Yoon Hyung Ho Lee 《Acta Crystallographica. Section D, Structural Biology》2015,71(10):2054-2065
The selection of correct metal ions with high fidelity against competing cellular cations is crucial for the function of many metalloenzymes; however, the understanding of the principles that govern metal selectivity is still incomplete. In this study, the crystal structure of the Tm1162 protein from Thermotoga maritima, a metallo‐β‐lactamase, is reported. Several crystal structures of wild‐type Tm1162 and its mutants were solved. Homologues of Tm1162 are widely distributed in bacteria and archaea, including several human pathogens. The monomer possesses an αβ/βα fold, with the core β‐strands having the β‐sheet sandwich structure common to the metallo‐β‐lactamase superfamily. Tm1162 exists as a trimer in the crystal and this trimeric unit is likely to be present in solution. In the trimer, three active sites reside at the interface between subunits, suggesting that the oligomeric assembly is crucial for catalysis. A new type of structurally encoded heterodinuclear site has been identified by confirming the identity of nickel‐containing heteronuclear sites in Tm1162 via X‐ray absorption spectroscopy and anomalous difference Fourier maps. The second coordination sphere, including His8 and Glu73, maintains the side‐chain orientations of histidines and stabilizes the metal‐binding site. Nickel coordination was crucial for the oligomerization of Tm1162. The nickel‐dependent and manganese‐dependent β‐lactamase and phosphodiesterase activities of Tm1162 have also been characterized. 相似文献
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Bacterial communities of some brown and red algae from Peter the Great Bay, the Sea of Japan 总被引:1,自引:0,他引:1
The structure of microbial communities of brown algae, red algae, and of the red alga Gracilaria verrucosa, healthy and affected with thallus rot, were comparatively investigated; 61 strains of heterotrophic bacteria were isolated and characterized. Most of them were identified to the genus level, some Vibrio spp., to the species level according to their phenotypic properties and the fatty acid composition of cellular lipids. The composition of the microflora of two species of brown algae was different. In Chordaria flagelliphormis, Pseudomonas spp. prevailed, and in Desmarestia viridis, Bacillus spp. The composition of the microflora of two red algae, G. verrucosa and Camphylaephora hyphaeoides, differed mainly in the ratio of prevailing groups of bacteria. The most abundant were bacteria of the CFB cluster and pseudoalteromonads. In addition, the following bacteria were found on the surface of the algae: Sulfitobacter spp., Halomonas spp., Acinetobacter sp., Planococcus sp., Arthrobacter sp., and Agromyces sp. From tissues of the affected G. verrucosa, only vibrios were isolated, both agarolytic and nonagarolytic. The existence of specific bacterial communities characteristic of different species of algae is suggested and the relation of Vibrio sp. to the pathological process in the tissues of G. verrucosa is supposed. 相似文献
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Zulipiya Shadike Hung‐Sui Lee Chuanjin Tian Ke Sun Liang Song Enyuan Hu Iradwikanari Waluyo Adrian Hunt Sanjit Ghose Yongfeng Hu Jigang Zhou Jian Wang Paul Northrup Seong‐Min Bak Xiao‐Qing Yang 《Liver Transplantation》2019,9(21)
An innovative organodisulfide compound, 2,3,4,6,8,9,10,12‐Octathia biscyclopenta[b,c]‐5,11‐anthraquinone‐1,7‐dithione (TPQD), has been successfully designed, synthesized, and characterized as a cathode material for lithium batteries. A benzoquinone is introduced to coordinate with dithiolane through 1,4‐dithianes. The molecular structure, electrochemical performances, and the lithiation/delithiation mechanism of the TPQD cathode have been systematically investigated. TPQD can deliver an initial capacity of 251.7 mAh g?1 at a rate of C/10, which corresponds to the transfer of 4.7 electrons per formula. Highly reversible capacities and stable cyclic performances can be achieved at rates from C/10 to 5 C. Very interestingly, TPQD can retain a capacity of 120 mAh g?1 after 200 cycles at the 5 C rate, which is quite impressive for organodisulfide compounds. X‐ray absorption spectroscopy measurements and density functional theory calculation results suggest that such a high capacity is contributed by both O redox of the quinone group and the cleavage and recombination of the disulfide bond. Moreover, the extended π‐conjugation structure of the material, introduced by benzoquinone and dithiane, is beneficial for improving the high rate capability and cyclic stability. This study illustrates an innovative approach in designing new organodisulfide compounds with improved cyclability and rate capability as cathode materials for high performance lithium batteries. 相似文献
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Christian Grundahl Frankr Marianne Vad Knudsen Katarina Norn Elena Nazarenko Kenny Sthl Pernille Harris 《Acta Crystallographica. Section D, Structural Biology》2012,68(10):1259-1271
The crystal structures of three conformations, T6, T3R3 and R6, of bovine insulin were solved at 1.40, 1.30 and 1.80 Å resolution, respectively. All conformations crystallized in space group R3. In contrast to the T6 and T3R3 structures, different conformations of the N‐terminal B‐chain residue PheB1 were observed in the R6 insulin structure, resulting in an eightfold doubling of the unit‐cell volume upon cooling. The zinc coordination in each conformation was studied by X‐ray absorption spectroscopy (XAS), including both EXAFS and XANES. Zinc adopts a tetrahedral coordination in all R3 sites and an octahedral coordination in T3 sites. The coordination distances were refined from XAS with a standard deviation of <0.01 Å. In contrast to the distances determined from the medium‐resolution crystal structures, the XAS results were in good agreement with similar coordination geometries found in small molecules, as well as in other high‐resolution insulin structures. As the radiation dose for XRD experiments is two orders of magnitude higher compared with that of XAS experiments, the single crystals were exposed to a higher degree of radiation damage that affected the zinc coordination in the T3 sites in particular. Furthermore, XANES spectra for the zinc sites in T6 and R6 insulin were successfully calculated using finite difference methods and the bond distances and angles were optimized from a quantitative XANES analysis. 相似文献
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Old and stable soil organic matter is not necessarily chemically recalcitrant: implications for modeling concepts and temperature sensitivity 总被引:2,自引:0,他引:2
MARKUS KLEBER PETER S. NICO ALAIN PLANTE TIMOTHY FILLEY MARC KRAMER CHRISTOPHER SWANSTON PHILLIP SOLLINS 《Global Change Biology》2011,17(2):1097-1107
Soil carbon turnover models generally divide soil carbon into pools with varying intrinsic decomposition rates. Although these decomposition rates are modified by factors such as temperature, texture, and moisture, they are rationalized by assuming chemical structure is a primary controller of decomposition. In the current work, we use near edge X‐ray absorption fine structure (NEXAFS) spectroscopy in combination with differential scanning calorimetry (DSC) and alkaline cupric oxide (CuO) oxidation to explore this assumption. Specifically, we examined material from the 2.3–2.6 kg L?1 density fraction of three soils of different type (Oxisol, Alfisol, Inceptisol). The density fraction with the youngest 14C age (Oxisol, 107 years) showed the highest relative abundance of aromatic groups and the lowest O‐alkyl C/aromatic C ratio as determined by NEXAFS. Conversely, the fraction with the oldest C (Inceptisol, 680 years) had the lowest relative abundance of aromatic groups and highest O‐alkyl C/aromatic C ratio. This sample also had the highest proportion of thermally labile materials as measured by DSC, and the highest ratio of substituted fatty acids to lignin phenols as indicated by CuO oxidation. Therefore, the organic matter of the Inceptisol sample, with a 14C age associated with ‘passive’ pools of carbon (680 years), had the largest proportion of easily metabolizable organic molecules with low thermodynamic stability, whereas the organic matter of the much younger Oxisol sample (107 years) had the highest proportion of supposedly stable organic structures considered more difficult to metabolize. Our results demonstrate that C age is not necessarily related to molecular structure or thermodynamic stability, and we suggest that soil carbon models would benefit from viewing turnover rate as codetermined by the interaction between substrates, microbial actors, and abiotic driving variables. Furthermore, assuming that old carbon is composed of complex or ‘recalcitrant’ compounds will erroneously attribute a greater temperature sensitivity to those materials than they may actually possess. 相似文献
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Seong‐Min Bak Ruimin Qiao Wanli Yang Sungsik Lee Xiqian Yu Babak Anasori Hungsui Lee Yury Gogotsi Xiao‐Qing Yang 《Liver Transplantation》2017,7(20)
2D vanadium carbide MXene containing surface functional groups (denoted as V2CTx , where Tx are surface functional groups) is synthesized and studied as anode material for Na‐ion batteries. V2CTx anode exhibits reversible charge storage with good cycling stability and high rate capability through electrochemical test. The charge storage mechanism of V2CTx material during Na+ intercalation/deintercalation and the redox reaction of vanadium are studied using a combination of synchrotron based X‐ray diffraction, hard X‐ray absorption near edge spectroscopy (XANES), and soft X‐ray absorption spectroscopy (sXAS). Experimental evidence of a major contribution of redox reaction of vanadium to the charge storage and the reversible capacity of V2CTx during sodiation/desodiation process are provided through V K ‐edge XANES and V L 2,3‐edge sXAS results. A correlation between the CO32? content and the Na+ intercalation/deintercalation states in the V2CTx electrode observed from C and O K ‐edge in sXAS results implies that some additional charge storage reactions may take place between the Na+‐intercalated V2CTx and the carbonate‐based nonaqueous electrolyte. The results of this study provide valuable information for the further studies on V2CTx as anode material for Na‐ion batteries and capacitors. 相似文献
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Benjamin L. Williams Jonathan D. Major Leon Bowen Wytze Keuning Mariadriana Creatore Ken Durose 《Liver Transplantation》2015,5(21)
This work presents the first systematic comparison of the effects of a range of chlorides (CdCl2, MgCl2, NaCl, and NH4Cl) on the microstructure and chemical composition of CdTe/CdS/ZnO/SnO2 solar cells, providing valuable insight to the ubiquitous Cl‐activation process. Using X‐ray diffraction, it is shown that CdCl2 induces the greatest extent of recrystallization (standard deviation of texture coefficients, σ, reduces from 0.93 for as‐grown CdTe to 0.43) and minimizing stress (from 178 MPa for as‐grown material to zero). MgCl2 treatment also yields significant randomization of the CdTe texture (σ = 0.55) but NaCl treatment does not (σ = 1.10). A strong correlation between the extent of metallurgical changes induced by the chloride treatment (and consequently, device efficiency) and the dissociation energy of the cationCl bond is shown, thereby accounting for the ineffectiveness of NaCl (bond energy = 4.3 eV). From this, a mechanism for Cl activation is postulated. By X‐ray photoelectron spectroscopy it is also shown that the Te/Cd ratio at the back surface, and the Cl content at the CdTe–CdS interface, are both higher following CdCl2‐ and MgCl2 treatments (Te/Cd = 1.3–1.4, and 1–2 at% Cl) than following NaCl treatment (Te/Cd = 1.1, and 0 at% Cl). 相似文献
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Sarawut Pongha Boonyarit Seekoaon Wanwisa Limphirat Pinit Kidkhunthod Sutham Srilomsak Yet‐Ming Chiang Nonglak Meethong 《Liver Transplantation》2015,5(15)
Dynamic phase transformation in olivine LiFePO4 involving formation of one or more intermediate or metastable phases is revealed by an in situ time‐resolved X‐ray absorption near edge structure (XANES) technique. The XANES spectra measured during relaxation immediately after the application of relatively high overpotentials, where metastable phases are expected, show a continuous shift of the Fe K‐edge toward higher energy. Surprisingly, the Fe K‐edge relaxes to higher energies after current interrupt regardless of whether the cell is being charged or discharged. This relaxation phenomenon is superimposed upon larger shifts in K‐edge due to changes in Fe2+/Fe3+ ratio due to charging and discharging, and implies an intermediate phase of larger Fe? O bond length than any of the known crystalline phases. No intermediate crystalline phases are observed by X‐ray diffraction (XRD). A metastable amorphous phase formed during dynamic cycling and which structurally relaxes to the equilibrium crystalline phases over a time scale of about 10 min after cessation of charging/discharging current is consistent with the experimental observations. 相似文献
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The X-ray crystallographic structure of a thioredoxin from Thermus thermophilus was solved to 1.8 A resolution by molecular replacement. The crystals' space group was C2 with cell dimensions of a = 40.91, b = 95.44, c = 56.68 A, beta =91.41 degrees, with two molecules in the asymmetric unit. Unlike the reported thioredoxin structures, the biological unit of T. thermophilus thioredoxin is a dimer both in solution and in the crystal. The fold conforms to the \"thioredoxin fold\" that is common over a class of nine protein families including thioredoxin; however, the folded portion of this protein is much more compact than other thioredoxins previously solved by X-ray crystallography being reduced by one alpha-helix and one beta-strand. As with other thioredoxins, the active site is highly conserved even though the variation in sequence can be quite large. The T. thermophilus thioredoxin has some variability at the active site, especially compared with previously solved structures from bacterial sources. 相似文献
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A novel Sn4P3/graphite composite anode material with superior capacity and cycling performance (651 mA h g?1 after 100 cycles) is investigated by in situ X‐ray absorption spectroscopy. Extended X‐ray absorption fine structure modeling and detailed analysis of local environment changes are correlated to the cell capacity and reveal the mechanism of lithiation/delithiation process. Results show that in the first two lithiation/delithiation cycles crystalline Sn4P3 is fully converted to an amorphous SnPx phase, which in further cycles participates in reversible conversion and alloying reactions. The superior reversibility of this material is attributed to the highly dispersed SnPx in the graphite matrix, which provides enhanced electrical conductivity and prevents aggregation of Sn clusters during the lithiation/delithiation process. The gradual capacity fading in long‐term cycling is attributed to the observed increase in the size and the amount of metallic Sn clusters in the delithiated state, correlated to the reduced recovery of the SnPx phase. This paper reveals the mechanism responsible for the highly reversible tin phosphides and provides insights for improving the capacity and cycle life of conversion and alloying materials. 相似文献