Time-resolved ultra-small-angle X-ray scattering beamline(BL10U1)at SSRF

The construction of a new beamline,BL10U1,was completed at the Shanghai synchrotron radiation facility in 2020.This multipurpose beamline was designed to provide X-ray scattering techniques such as ultra-small-angle X-ray scattering(USAXS),small-angle X-ray scattering(SAXS),wide-angle X-ray scattering,and microfocus SAXS(μSAXS)for a broad user community.To realize fast time-resolved USAXS experiments,the beamline adopted an in-vacuum undulator with a total length of 1.6 m as the photon source.An in-house cryogenic-cooled double multilayer monochromator was installed to deliver a photon flux of approximately 10^(13) photons/s at a photon energy of 10 keV.The three-year successful operation of this beamline demonstrated that the monochromator operated smoothly,as expected.BL10U1 has three end stations in succession:USAXS end station,μSAXS end station,and end station for industrial applications.The minimum scattering vector q~0.0042 nm^(-1) at 10 keV can be achieved at the USAXS end station equipped with a 28 m-long and 1.8 m-diameter vacuum flight tube.At theμSAXS end station,a beam spot of less than 10×8μm was achieved for micro-SAXS experiments.In contrast,in situ experimental instruments up to 5 m high and 8 m wide can be mounted at the industrial application end station,which offers industrial scientists the opportunity to use their large industrial equipment.BL10U1 opens up a new capability to investigate phenomena such as non-equilibrium and dynamic processes of materials with a wide length scale from angstroms to micrometers with millisecond time resolution.In this paper,we also report beamline design considerations and commissioning results.

BL19U2:Small-angle X-ray scattering beamline for biological macromolecules in solution at SSRF

The BL19U2 at the Shanghai Synchrotron Radiation Facility is a small-angle X-ray scattering beamline dedicated to structural studies pertaining to biological macromolecules in solution.The beamline has been officially opened to users in March 2015,and since then,a series of technological innovations has been developed to optimize beamline performance,thereby significantly improving the data collection efficiency and broadening the application scope of biological small-angle X-ray scattering.BL19U2 is ideal for the high-throughput screening of weakly scattered proteins,protein assemblies,nucleic acids,inorganic nanomaterials,and organic drug molecules.This paper describes the design and overview of the BL19U2 beamline.Versatile sample environments at the experimental station and some recent scientific highlights are presented.

Understanding fluorine-free electrolytes via small-angle X-ray scattering

Fluorine-free electrolytes have attracted great attention because of its low-cost and environmental friendliness. However, so far, little is known about the solution structures of these electrolytes. Here,we compare the solvation phenomenon of sodium tetraphenylborate(NaBPh_(4)) salt dissolved in organic solvents of propylene carbonate(PC), 1,2-dimethoxyethane(DME), acetonitrile(ACN) and tetrahydrofuran(THF). Small-angle X-ray scattering(SAXS) reveals a unique two-peak structural feature in this saltconcentrated PC electrolyte, while solutions using other solvents only have one scattering peak.Molecular dynamics(MD) simulations further reveal that there are anion-based clusters in addition to the short-range charge ordering in the concentrated NaBPh4/PC electrolyte. Raman spectroscopy confirms the existence of considerable contact ion pairs(CIPs). This work emphasizes the importance of global and local structural analysis, which will provide valuable clues for understanding the structureperformance relationship of electrolytes.

Structural modeling of proteins by integrating small-angle x-ray scattering data

Elucidating the structure of large biomolecules such as multi-domain proteins or protein complexes is challenging due to their high flexibility in solution. Recently, an ＂integrative structural biology＂ approach has been proposed, which aims to determine the protein structure and characterize protein flexibility by combining complementary high- and lowresolution experimental data using computer simulations. Small-angle x-ray scattering（SAXS） is an efficient technique that can yield low-resolution structural information, including protein size and shape. Here, we review computational methods that integrate SAXS with other experimental datasets for structural modeling. Finally, we provide a case study of determination of the structure of a protein complex formed between the tandem SH3 domains in c-Cb1-associated protein and the proline-rich loop in human vinculin.

In-situ study of precipitates in Al–Zn–Mg–Cu alloys using anomalous small-angle x-ray scattering

In the present work,the precipitate compositions and precipitate amounts of these elements（including the size distribution,volume fraction,and inter-precipitate distance） on the Cu-containing 7000 series aluminum alloys（7150 and 7085 Al alloys）,are investigated by anomalous small-angle x-ray scattering（ASAXS） at various energies.The scattering intensity of 7150 alloy with T6 aging treatment decreases as the incident x-ray energy approaches the Zn absorption edge from the lower energy side,while scattering intensity does not show a noticeable energy dependence near the Cu absorption edge.Similar results are observed in the 7085 alloy in an aging process（120℃） by employing in-situ ASAXS measurements,indicating that the precipitate compositions should include Zn element and should not be strongly related to Cu element at the early stage after 10 min.In the aging process,the precipitate particles with an initial average size of ~ 8 ？A increase with aging time at an energy of 9.60 ke V,while the increase with a slower rate is observed at an energy of 9.65 ke V as near the Zn absorption edge.

Investigation of the topological shape of bovine serum albumin in solution by small-angle x-ray scattering at Beijing synchrotron radiation facility

This paper reports that at a newly constructed small-angle x-ray scattering station of Beijing Synchrotron Radia- tion Facility, the topological shape of ligand-free bovine serum albumin in solution has been investigated. An appropriate scattering curve is obtained and the calculated value of the gyration radius is 31.2~=t=0.25 ~_ （11=0.1 nm） which is co- incident with other ones＇ results. It finds that the low-resolution structure models obtained by making use of ab initio reconstruction methods are fitting the crystal structure of human serum albumin very well. All of these results perform the potential of the beamline to apply to structural biology studies. The characteristics, the defects, and the improving measures of the station in future are also discussed.

Small-Angle X-Ray Scattering of Amorphous Germanium: Numerical Modeling

The present work deals with a detailed analysis of the small-angle X-ray scattering of nanoporous atomistic models for amorphous germanium. Structures with spherical nanovoids, others with arbitrarily oriented ellipsoidal ones, with monodisperse and polydisperse size distributions, were first generated. After relaxing the as-generated structure, we compute its radial distribution function, and then we deduce by the Fourier transform technique its X-ray scattering pattern. Using a smoothing procedure, the computed small-angle X-ray scattering patterns are corrected for the termination errors due to the finite size of the model, allowing so, for the first time at our best knowledge, a rigorous quantitative analysis of this scattering. The Guinier’s law is found to be valid irrespective of size and shape of the nanovoids over a scattering vector-range extending beyond the expected limit. A weighted combination of the Guinier’s forms accounts for well the nanovoid size distribution in the amorphous structure. The invariance of the Q-factor and its relationship to the void volume fraction are also confirmed. Our findings support then the quantitative analyses of available small-angle X-ray scattering data for amorphous germanium.

The Significance of Solutions Obtained from Ill-Posed Systems of Linear Equations Constituted by Synchrotron Radiation Based Anomalous Small-Angle X-Ray Scattering

Synchrotron radiation based experimental techniques known as Anomalous Small-Angle X-ray Scattering (ASAXS) provide deep insight into the nanostructure of uncountable material systems in condensed matter research i.e. solid state physics, chemistry, engineering and life sciences thereby rendering the origin of the macroscopic functionalization of the various materials via correlation to its structural architecture on a nanometer length scale. The techniques constitute a system of linear equations, which can be treated by matrix theory. The study aims to analyze the significance of the solutions of the stated matrix equations by use of the so-called condition numbers first introduced by A. Turing, J. von Neumann and H. Goldstine. Special attention was given for the comparison with direct methods i.e. the Gaussian elimination method. The mathematical roots of ill-posed ASAXS equations preventing matrix inversion have been identified. In the framework of the theory of von Neumann and Goldstine the inversion of certain matrices constituted by ASAXS gradually becomes impossible caused by non-definiteness. In Turing’s theory which starts from more general prerequisites, the principal minors of the same matrices approach singularity thereby imposing large errors on inversion. In conclusion both theories recommend for extremely ill-posed ASAXS problems avoiding inversion and the use of direct methods for instance Gaussian elimination.

Real-time pore structure evolution difference between deep and shallow coal during gas adsorption:A study based on synchrotron radiation small-angle X-ray scattering

Coal seam CO_(2) sequestration is an important option to address global warming.A better knowledge on coal pore structure evolution during gas adsorption can provide guidance for coal seams CO_(2) seques-tration.However,few investigations on the pore structure evolution differences between the deep and shallow coal were conducted during gas adsorption.In this study,based on the real-time synchrotron radiation small-angle X-ray scattering(SAXS)observation,the average pore diameter and pore surface fractal dimension evolution differences between deep and shallow coal were investigated from the as-pects of coal compositions and stress history.Two types of coal deformation(inner-swelling and outer-swelling)coexist during gas adsorption.Coal compositions have significant impact on the dominance of deformation type.The dominance of inner-swelling in deep coal is induced by the higher ash contents,and there is the decrease of average pore diameter during gas adsorption.The impact of stress-history(burial depth)on adsorption-induced deformation is more prominent than that of gas adsorption ca-pacity.In deep coal,the surface fractal dimension evolution presents a negative correlation with the evolution of pore diameters.In shallow coal,the surface fractal dimension evolution presents a Langmuir-type correlation with the adsorption time.

Small-angle X-ray analysis of the effect of grain size on the thermal damage of octahydro-1, 3, 5, 7-tetranitro-1, 3, 5, 7 tetrazocine-based plastic-bounded expolsives

The microstmcture evolution of plastic-bonded explosives （PBXs） after thermal stimulus plays a key role in PBX performance. In this paper, the nanoscale pores of thermal-treated octahydro-1,3,5,7-tetranitro-1,3,5,7 tetrazocine （HMX）- based PBXs with different HMX particle sizes [approximately 40 （FLIP） and 100 μm （LHP）] were measured using small- angle X-ray scattering （SAXS）. No obvious pore variations were found in the LHP samples heated at 160 ℃ for 6 h, whereas the amount of pores of FHP decreased when subjected to 160 ℃ for 6 h. At 180 ℃, the average pore radii of FHP and LHP decreased from approximately 45 nm to 25 nm, and the total pore volume increased distinctively because of phase transformation. The LHP sample reached a high level of pore content after being held at 180 ℃ for 1 h, whereas FHP required 3 h. Both FHP and LHP had relatively high pore volumes when subjected to 200 ℃ for 1 and 3 h.

INVESTIGATION ON THE CONFORMATION OF THE MAIN-CHAIN NEMATIC POLYMER BY SMALL ANGLE X-RAY SCATTERING

The experimental investigation on the conformation of a thermotropic main-chain nematic polymer by small-angle X-ray scattering (SAXS) has been carried out. The average radius of gyration of the polymer has been determined in nematic and isotropic state respectively. The experiment shows that the boundary between domains is not sharp but diffuse, and the diffuse-boundary thickness of the polymer as a function of temperature has been given.

Grazing-incidence small-angle X-ray scattering property of double-layered gold nanoparticle arrays

Gold nanoparticle arrays fabricated via layerby-layer technique were investigated using grazing-incidence small-angle X-ray scattering(GISAXS) method.Samples containing two gold nanoparticle layers that were separated by 5,11,15 and 21 poly electrolyte(PE) interlayers were studied.By using different X-ray incident angles,correlations of gold nanoparticles(GNPs) in the same layer and in two different layers were investigated.It is found that both sideway correlations between GNPs in the same layer and vertical correlation between two gold nanoparticle layers depend on the thickness of PE interlayers.According to sideway correlation,the size of GNPs is determined to be(13.0±0.5) nm in all of the four samples,which was also proved by scanning electron microscopy(SEM) and theoretical calculation of form factor of spherical particles.From vertical correlation,distance between two gold nanoparticle layers was determined for sample with 11,15 and 21 PE layers.These distances can be reasonably explained with the number of PE layers and the thickness of single PE layer.These results indicate that by repeated depositing of oppositely charged PE layers,a true three-dimensional(3 D) nanostructure can eventually be designed.

Complexation of DNA with cationic surfactants as studied by small-angle X-ray scattering

The phase behaviors of the complex formed by didodecyldimethylammonium bromide（DDAB）and cetyltrimethylammonium bromide（CTAB）interacting with three different types of DNAs,salmon testes DNA（~2000 bp）,21-bp double-stranded oligonucleotides（oligo-ds DNA）,and 21-nt single-stranded oligonucleotides（oligo-ss DNA）were studied by synchrotron small-angle X-ray scattering.It was found that the DNA length and flexibility,together with the positive/negative charge ratio,determined the final structure.At higher charge ratios,the DNA length exhibited negligible effect.Both oligo-ds DNA and salmon DNA formed inverted hexagonal packing of cylinders with CTAB,as well as bilayered lamella with DDAB.However,at lower charge ratios,oligo-ds DNA formed a distorted hexagonal phase with CTAB and a new structure with DDAB,which was different from the behaviors of salmon DNA.The flexible oligo-ss DNA formed rich structures that were subject to environmental disturbance.Kinetic study also indicated that the structures of the complex formed by oligo-ss DNA took much longer to mature than the structures formed by oligo-ds DNA.We attributed this result to the conformational adjustment of oligo-ss DNA in the complex.

In situ grazing-incidence small-angle X-ray scattering observation of block-copolymer templated formation of magnetic nanodot arrays and their magnetic properties

The fabrication of bit-patterned media （BPM） is crucial for new types of hard disk drives. The development of methods for the production of BPM is progressing rapidly. Conventional lithography reaches the limit regarding lateral resolution, and new routes are needed. In this study, we mainly focus on the dependence of the size and shape of magnetic nanodots on the Ar＋-ion etching duration, using silica dots as masks. Two-dimensional （2D） arrays of magnetic nanostructures are created using silica-filled diblock-copolymer micelles as templates. After the self-assembly of the micelles into 2D hexagonal arrays, the polymer shell is removed, and the SiO2 cores are utilized to transform the morphology into a （Co/Pt）2-multilayer via ion etching under normal incidence. The number of preparation steps is kept as low as possible to simplify the formation of the nanostructure arrays. High-resolution in situ grazing-incidence small-angle X-ray scattering （GISAXS） investigations are performed during the Ar＋-ion etching to monitor and control the fabrication process. The in situ investigation provides information on how the etching conditions can be improved for further ex situ experiments. The GISAXS patterns are compared with simulations. We observe that the dots change in shape from cylindrical to conical during the etching process. The magnetic behavior is studied by utilizing the magneto-optic Kerr effect. The Co/Pt dots exhibit different magnetic behaviors depending on their size, interparticle distance, and etching time. They show ferromagnetism with an easy axis of magnetization perpendicular to the film. A systematic dependence of the coercivitv on the dot size is observed.

DETERMINATION OF THE SPECIFIC INNER SURFACE OF CRYSTALLINE-AMORPHOUS TWO-PHASE SYSTEM BY SMALL-ANGLE X-RAY SCATTERING

The specific inner surface, S_p, of the crystalline-amorphous 2-phase system inCu_(73)Sn_6Ni_6P_(15) metallic glass, aged at 473 K, was determined by small-angle X-ray scatteringand wide-angle X-ray diffraction. The experimental results show that the specific innersurface decreases from 144 m^2/cm^3 to 96 m^2/cm^3 as aging period increases from 5 min to 4 h.The error of S_p values is about 7%.

Microfocus small-angle X-ray scattering at SSRF BL16B1

Offering high-brilliance X-ray beams on micrometer length scales,the μSAXS at SSRF BL16 B1 has been established with a KB mirror system for studying small sample volumes,or probing microscopic morphologies.The SAXS minimum q value is 0.1 nm^-1 with a flux of 1.5×10^10 photons/s.Two position-resolved scanning experimental methods,STXM and CT,are combined with μSAXS.To improve the significant smearing effect in the horizontal direction,an effective and easy-to-use desmearing procedure for two-dimensional SAXS patterns based on blind deconvolution was developed,and the deblurring results demonstrate the good restoration effect for the defocused image.Finally,a bamboo sample was used in the SAXS-CT experiment to illustrate the performance of the μSAXS method.

Small-angle X-ray scattering probe of intermolecular interaction in red blood cells

With high concentrations of hemoglobin （Hb） in red blood cells, self-interactions among these molecules could increase the propensities of their polymerization and aggregation. In the present work, high concentration Hb in solution and red blood cells were analyzed by small-angle X-ray scattering. Calculation of the effective structure factor indicates that the interaction of Hb molecules is the same when they are crowded together in both the cell and physiological saline. The Hb molecules stay individual without the formation of aggregates and clusters in cells.

A simple vacuum sample chamber for small-angle X-ray scattering at Beijing synchrotron radiation facility

Objective A vacuum sample chamber for SAXS measurement of solutions was developed to improve the signal-to-noise ratio of the instrument at Beijing Synchrotron Radiation Facility(BSRF).Methods We developed a vacuum sample chamber which could be connected to the upstream and the downstream vacuum tubes by bellows.Horizontal and vertical linear slides were mounted in the vacuum chamber to adjust the sample position by 35 mm in the horizontal and vertical directions to align the sample in the light path.The liquid sample holder of the chamber was sealed with polyimide film by squeezing instead of gluing to avoid the potential influence of sealant on the solution.Results The chamber had been used for SAXS measurements of water and bovine serum albumin solution at BSRF.The results showed that the background scattering intensity in air was much higher than that in vacuum,especially in the smallangle area near the beamstop.When the q value is 0.142 nm−1,1.01 nm−1 and 1.25 nm−1,the background scattering intensity in air is 45,6.8 and 4.6 times of that in vacuum,respectively.And the background-subtracted scattering curves of bovine serum albumin solution(10 mg/ml)in air and vacuum differ in intensity by a factor of about 2.When the q value is 2 nm−1,the signal-to-noise ratios of scattering intensity of BSA in air and vacuum are 0.79 and 8.51,respectively.Conclusion We designed a simple vacuum sample chamber to be used on the SAXS instrument at 1W2A station of BSRF.The scattering of the background and protein solution in air and vacuum was tested and compared,and the signal-to-noise ratio was clearly improved.

Active precursor promoting nucleation/growth of MwW zeolite and controlling its morphology

MWW zeolites is an important catalyst in petrochemical industry.However,the efficient preparation of Mww zeolites still faces challenges,and the origin of influential factors for regulating its structure properties also remains obscure.Herein,we designed a nanoscale amorphous silica-alumina species denoted as active precursor(APS),and adopt the APS in the HMI mixture to synthesize MCM-22 zeolite(APS-MWW)successfully.To reveal the distinctive role of APS in promoting the crystallization of MWW zeolites,two crystal materials(ITQ-1 and MCM-22)and one mother liquor(ML)as seeds to synthesize three types of MWW zeolites.Typically,when adding APS in the synthetic mixture,the HMI amount was reduced to less than a quarter and crystallization time was reduced to 36 h.APS-MWW sample provides a smaller particle size(2-4μm)and thinner stacked layer thickness(5-20 nm).Synchrotron radiation Small Angle X-ray Scattering(SAXS)shows each seed has a different impact on the species'fractal structure and size distribution in the mixture,which is highly related to the nucleation and growth of MWW zeolites.APS shows a large number of 6 membered ring(MR)structure units which play a sig-nificant role in boosting the rapid nucleation and growth of APS-MwW zeolite.Among the synthesized MWW zeolites,the APS-MWW performs the highest ethylbenzene yield in the alkylation reaction of benzene-ethylene,which is attributed to its moderate flake thickness,appropriate texture properties and more external surface acidity.The results will provide a new perspective for producing MwW-types zeolites by using the available and effective active precursor.

In situ observation of synthesized nanoparticles in ultra-dilute aerosols via X-ray scattering

In-air epitaxy of nanostructures(Aerotaxy)has recently emerged as a viable route for fast,large-scale production.In this study,we use small-a ngle X-ray scatteri ng to perform direct in-flight characterizati ons of the first step of this process,i.e.,the en gineered formatio n of Au and Pt aerosol nan oparticles by spark gen erati on in a flow of N2 gas.This represe nts a particular challe nge for characterizati on because the particle density can be extremely low in con trolled production.The particles produced are exami ned duri ng producti on at operatio nal pressures close to atmospheric conditions and exhibit a log no rmal size distributi on ranging from 5-100nm.The Au and Pt particle productio n and detection are compared.We observe and characterize the nanoparticles at different stages of synthesis and extract the corresponding domi nant physical properties,in cludi ng the average particle diameter and sphericity,as in flue need by particle sintering and the prese nee of aggregates.We observe highly sorted and sin tered spherical Au nano particles at ultra-dilute concen tratio ns(<5×10^5 particles/cm^3)corresponding to a volume fraction below 3×10^-10,which is orders of magnitude below that of previously measured aerosols.We independently confirm an average particle radius of 25 nm via Guinier and Kratky plot analysis.Our study indicates that with high-intensity synchrotron beams and careful con sideratio n of backgro und removal,size and shape info rmati on can be obtai ned for extremely low particle concentrations with industrially relevant narrow size distributions.